Development and validation of a confirmative LC-MS/MS method for the determination of ß-exotoxin thuringiensin in plant protection products and selected greenhouse crops

Bacterial products based on Bacillus thuringiensis are registered in many countries as plant protection products (PPPs) and are widely used as insecticides and nematocides. However, certain B. thuringiensis strains produce harmful toxins and are therefore not allowed to be used as PPPs. The serotype B. thuringiensis thuringiensis produces the beta-exotoxin thuringiensin (ßeT) which is considered to be toxic for almost all forms of life including humans (WHO 1999). The use of a non-registered PPP based on B. thuringiensis thuringiensis called bitoxybacillin was established through the determination of ßeT. First, an analytical reference standard of ßeT was characterized by nuclear magnetic resonance, liquid chromatography–high-resolution mass spectrometry and liquid chromatography–tandem mass spectrometry (LC-MS/MS). Then, a confirmatory quantitative method for the determination of ßeT in PPPs and selected greenhouse crops based on LC-MS/MS was developed and validated. A limit of quantitation of 0.028 mg/kg was established, and average recoveries ranged from 85.6 % to 104.8 % with repeatability (RSDr) of 1.5–7.7 % and within-lab reproducibility (RSD_WLR) of 17 %. The method was used for analysis of >100 samples. ßeT was found in leaves of ornamentals, but no evidence was found for use in edible crops.

An iterative thresholding algorithm for linear inverse problems with a sparsity constraint

We consider linear inverse problems where the solution is assumed to have a sparse expansion on an arbitrary preassigned orthonormal basis. We prove that replacing the usual quadratic regularizing penalties by weighted ??^p‐penalties on the coefficients of such expansions, with 1 ≤ p ≤ 2, still regularizes the problem. Use of such ??^p‐penalized problems with p < 2 is often advocated when one expects the underlying ideal noiseless solution to have a sparse expansion with respect to the basis under consideration. To compute the corresponding regularized solutions, we analyze an iterative algorithm that amounts to a Landweber iteration with thresholding (or nonlinear shrinkage) applied at each iteration step. We prove that this algorithm converges in norm. © 2004 Wiley Periodicals, Inc.     

A Thermodynamic Approach to Measuring Entropy in a Few-Electron Nanodevice

The entropy of a system gives a powerful insight into its microscopic degrees of freedom; however, standard experimental ways of measuring entropy through heat capacity are hard to apply to nanoscale systems, as they require the measurement of increasingly small amounts of heat. Two alternative entropy measurement methods have been recently proposed for nanodevices: through charge balance measurements and transport properties. We describe a self-consistent thermodynamic framework for applying thermodynamic relations to few-electron nanodevices—small systems, where fluctuations in particle number are significant, whilst highlighting several ongoing misconceptions. We derive a relation (a consequence of a Maxwell relation for small systems), which describes both existing entropy measurement methods as special cases, while also allowing the experimentalist to probe the intermediate regime between them. Finally, we independently prove the applicability of our framework in systems with complex microscopic dynamics—those with many excited states of various degeneracies—from microscopic considerations.     

Validation of a qualitative screening method for pesticides in fruits and vegetables by gas chromatography quadrupole-time of flight mass spectrometry with atmospheric pressure chemical ionization

A wide-scope screening method was developed for the detection of pesticides in fruit and vegetables. The method was based on gas chromatography coupled to a hybrid quadrupole time-of-flight mass spectrometer with an atmospheric pressure chemical ionization source (GC-(APCI)QTOF MS). A non-target acquisition was performed through two alternating scan events: one at low collision energy and another at a higher collision energy ramp (MS^E). In this way, both protonated molecule and/or molecular ion together with fragment ions were obtained in a single run. Validation was performed according to SANCO/12571/2013 by analysing 20 samples (10 different commodities in duplicate), fortified with a test set of 132 pesticides at 0.01, 0.05 and 0.20 mg kg⁻¹. For screening, the detection was based on one diagnostic ion (in most cases the protonated molecule). Overall, at the 0.01 mg kg⁻¹ level, 89% of the 2620 fortifications made were detected. The screening detection limit for individual pesticides was 0.01 mg kg⁻¹ for 77% of the pesticides investigated. The possibilities for identification according to the SANCO criteria, requiring two ions with a mass accuracy ≤±5 ppm and an ion-ratio deviation ≤±30%, were investigated. At the 0.01 mg kg⁻¹ level, identification was possible for 70% of the pesticides detected during screening. This increased to 87% and 93% at the 0.05 and 0.20 mg kg⁻¹ level, respectively. Insufficient sensitivity for the second ion was the main reason for the inability to identify detected pesticides, followed by deviations in mass accuracy and ion ratios.     

A Method for Solving Two-Dimensional Nonlinear Boundary-Value Problems of Magnetoelasticity for Thin Shells

A method is proposed to solve two-dimensional nonlinear problems of magnetoelasticity for thin shells. A problem is formulated and two-dimensional nonlinear equations of magnetoelasticity for current-carrying shells are derived__________Translated from Prikladnaya Mekhanika, Vol. 41, No. 5, pp. 32–39, May 2005.     

Setting-up early computer programs: D. H. Lehmer’s ENIAC computation

A complete reconstruction of Lehmer’s ENIAC set-up for computing the exponents of p modulo two is given. This program served as an early test program for the ENIAC (1946). The reconstruction illustrates the difficulties of early programmers to find a way between a man operated and a machine operated computation. These difficulties concern both the content level (the algorithm) and the formal level (the logic of sequencing operations).     

First enantioselective synthesis of isagarin,a natural product isolated from Pentas longiflora Oliv.

For the first time, an enantioselective synthesis of both 1R,4S-isagarin 1a and 1S,4R-isagarin 1b was achieved starting from 1,4-dimethoxy-2-vinylnaphthalene 2. The key steps involve a Sharpless asymmetric dihydroxylation and reaction with an acetonylating pyridinium ylid. The different optical rotations and melting points of the enantiopure 1R,4S-isagarin 1a and 1S,4R-isagarin 1b with respect to the isolated natural product will be addressed.