Degradation of parathion methyl on field-sprayed apples and stored apples

Residue levels of parathion methyl on field-sprayed Granny-Smith apples were studied. The pesticide was applied according to producer recommendations. Apples received a single spraying at a rate of 40 g active ingredient/100 L. Residues were determined with a simple gas chromatographic method. Recovery of parathion methyl was 88-108%, and the limit of determination was 0.002 mg/kg. Decomposition of parathion methyl was studied in apples remaining on trees after spraying and in apples harvested and stored under ambient-temperature, refrigerated-room, and controlled-atmosphere conditions. During post harvest storage, parathion methyl degrades more slowly than on apples remaining on the trees. Best-fit curves were determined, and kinetic equations, rate constants, and half-lives were calculated. Half-lives found were 8 days for apples on trees, 45 days for apples stored at ambient conditions, 68 days for apples stored in controlled-atmosphere room, and 62 days for apples stored in a refrigerated room. Under storage conditions, levels of parathion methyl residues need a long time to become lower than the legal limit (0.2 mg/kg).     

Optimal Regularity of Lower-Dimensional Obstacle Problems

In this paper, we prove that solutions to the “boundary obstacle problem” have the optimal regularity, C^1,1/2, in any space dimension. This bound depends only on the local L²-norm of the solution. Main ingredients in the proof are the quasiconvexity of the solution and a monotonicity formula for an appropriate weighted average of the local energy of the normal derivative of the solution. Bibliography: 8 titles. Dedicated to Nina Nikolaevna Uraltseva on the occasion of her 70th birthday __________ Published in Zapiski Nauchnykh Seminarov POMI, Vol. 310, 2004, pp. 49–66.     

Precise mass measurement of a double-stranded 500 base-pair (309 kDa) polymerase chain reaction product by negative ion electrospray ionization Fourier transform ion cyclotron resonance mass spectrometry

Electrospray ionization Fourier transform ion cyclotron resonance mass spectrometry (ESI-FTICRMS) has been used to determine the mass of a double-stranded 500 base-pair (bp) polymerase chain reaction (PCR) product with an average theoretical mass of the blunt-ended (i.e. unadenylated) species of 308 859.35 Da. The PCR product was generated from the linearized bacteriophage Lambda genome which is a double-stranded template. Utilization of ethanol precipitation in tandem with a rapid microdialysis step to purify and desalt the PCR product was crucial to obtain a precise mass measurement. The PCR product (0.8 pmol/μL) was electrosprayed from a solution containing 75% acetonitrile, 25 mM piperidine, and 25 mM imidazole and was infused at a rate of 200 nL/min. The average molecular mass and the corresponding precision were determined using the charge-states ranging from 172 to 235 net negative charges. The experimental mass and corresponding precision (reported as the 95% confidence interval of the mean) was 309 406 +/- 27 Da (87 ppm). The mass accuracy was compromised due to the fact that the PCR generates multiple products when using Taq polymerase due to the non-template directed 3'-adenylation. This results in a mixture of three PCR products with nearly identical mass (i.e. blunt-ended, mono-adenylated and di-adenylated) with unknown relative abundances that were not resolved in the spectrum. Thus, the experimental mass will be a weighted average of the three species which, under our experimental conditions, reflects a nearly equal concentration of the mono- and di-adenylated species. This report demonstrates that precise mass measurements of PCR products up to 309 kDa (500 bp) can be routinely obtained by ESI-FTICR requiring low femtomole amounts. Copyright 1999 John Wiley & Sons, Ltd.     

Effect of storage temperature on degradation of methidathion in fortified orange and peach juices

The effect of storage temperature on methidathion degradation in orange and peach juices was studied. The insecticide was aseptically added to packed orange and peach juices, which were stored at 40, 15, and 0 degrees C. Samples were taken at regular intervals and examined for residues of methidathion. Residues were determined with a simple gas chromatographic method; recoveries of methidathion from orange and peach juices ranged from 88.1 to 110% for both juices, and the limits of determination were 0.004 and 0.003 mg/kg, respectively. The experimental data were used to evaluate rate constants, half-lives, and times required to reach legal maximum residue limits, and activation energies for the decomposition of methidathion in orange and peach juices. Storage of fruit juices in refrigerated rooms greatly extended the half-life of methidathion beyond that of methidathion in samples stored at higher temperatures. Half-life values for methidathion in orange and peach juices, respectively, were 4.1 and 3.8 days for storage at 40 degrees C, 115 and 113 days for storage at 15 degrees C, and 330 and 385 days for storage at 0 degrees C. Activation energies for methidathion degradation in orange and peach juices were 22.6 and 21.7 kcal/mol, respectively.     

Investigation of the quantitative properties of the quadrupole orthogonal acceleration time-of-flight mass spectrometer with electrospray ionisation using 3,4-methylenedioxymethamphetamine

This paper describes the investigation of the potential of a quadrupole orthogonal acceleration time-of-flight mass spectrometer (Q-TOF) equipped with an atmospheric pressure ionisation interface for quantitative measurements of small molecules separated by reversed phase liquid chromatography. To this end, the detection limits and linear dynamic range in particular were studied in an LC/MS/MS experiment using 3,4-methylenedioxymethamphetamine standards and 3,4-methylenedioxyethylamphetamine for internal standardisation. In a second phase, the experiment was repeated with real biological extracts (whole blood, serum, and vitreous humour). A calibration for 3,4-methylenedioxymethamphetamine and its metabolite 3,4-methylenedioxyamphetamine was prepared in each of these matrices again using 3,4-methylenedioxyethylamphetamine as internal standard. The resulting quantitative data were compared with those obtained by liquid chromatography with fluorescence detection for the same extracts. The Q-TOF results revealed excellent sensitivity and a linear dynamic range of nearly four decades (2-10 000 pg on-column, r(2) = 0.9998, 1/x weighting). Furthermore, all the calibration curves prepared in biological material were superimposable, LC/MS/MS and LC-fluorescence, and the quantitative results for actual samples compared very favourably. It was concluded that the Q-TOF achieves a linear dynamic range for quantitative LC/MS/MS work exceeding that of fluorescence detection and at much better absolute sensitivity. Copyright 1999 John Wiley & Sons, Ltd.