Uncertainties in the determination of pyrrolizidine alkaloid levels in naturally contaminated honeys and comparison of results obtained by different analytical approaches

The contamination of honey with hepatotoxic pyrrolizidine alkaloids (PAs) is a well-known hazard for food safety. While management strategies and controls of the honey industry aim to reduce the PA levels, uncertainties remain with regard to the safety of regionally produced and marketed honey. In addition, a previous study showed large differences of results obtained after various periods of storage and apparent differences between the analytical results of different laboratories. Therefore, this study aimed at examining these uncertainties by monitoring the impact of storage on the PA and PA N-oxide (PANO) content of two freshly harvested honeys and on possible demixing effects caused by pollen settling. Additionally, three analytical approaches – target analysis with matrix-matched calibration or standard addition and a sum parameter method – were applied for a comparative analysis of 20 honeys harvested in summer 2016. All samples originated from Schleswig-Holstein in Northern Germany where the PA plant Jacobaea vulgaris is currently observed on a massive scale. The results of the time series analyses showed that PANO levels markedly decreased within a few weeks and practically reached the LOD 16 weeks after harvest. Tertiary PAs, by contrast, remained stable and did not increase as a consequence of PANO decrease. The experiments on a putative demixing, which may result in a heterogeneous distribution of PAs/PANOs, revealed that there was no such effect during storage of up to 12 weeks. A comparison of the PA/PANO levels obtained by different analytical approaches showed that in some cases the sum parameter method yielded much higher levels than the target approaches, whereas in other cases, the target analysis with standard addition found higher levels than the other two methods. In summary, the results of this study highlight uncertainties regarding the validity and comparability of analytical results and consequently regarding health risk assessment.     

Mixed Mode VLSI Implementation of a Neural Associative Memory

A mixed mode digital/analog special purpose VLSI hardware implementation of an associative memory with neural architecture is presented. The memory concept is based on a matrix architecture with binary storage elements holding the connection weights. To enhance the processing speed analog circuit techniques are applied to implement the algorithm for the association. To keep the memory density as high as possible two design strategies are considered. First, the number of transistors per storage element is kept to a minimum. In this paper a circuit technique that uses a single 6-transistor cell for weight storage and analog signal processing is proposed. Second, the device precision has been chosen to a moderate level to save area as much as possible. Since device mismatch limits the performance of analog circuits, the impact of device precision on the circuit performance is explicitly discussed. It is shown that the device precision limits the number of rows activated in parallel. Since the input vector as well as the output vector are considered to be sparsely coded it is concluded, that even for large matrices the proposed circuit technique is appropriate and ultra large scale integration with a large number of connection weights is feasible.     

Sequential Decoding of Convolutional Codes for Rayleigh Fading Channels

The performance of sequential decoding of long constraint length convolutional codes is evaluated for Rayleigh fading channels. Sequential decoding is not practical below a certain theoretical signal-to-noise ratio, and these theoretical limits are calculated for a number of modulation methods and code rates. As an example, with BPSK modulation, soft decisions and code rate 1/2, the theoretical signal-to-noise ratio per information bit is 5.7 dB. Above this limit the bit error rate can be made arbitrarily small by increasing the constraint length at no significant complexity cost. Furthermore, it is shown that with carefully chosen quantization steps, 8 level uniform quantization gives a negligible loss also for sequential decoding on a Rayleigh fading channel. Simulation results using 8 level quantization correspond well with the theoretical performance bounds. Also, the performance on a correlated channel with finite interleaving has been obtained. With an interleaver depth of 50×50 and a normalized doppler frequency equal to 0.01 we are only 0.5 dB away from the performance with perfect interleaving. Finally, bit error rate results show this scheme to compete well with Turbo codes.     

Model reactions on roast aroma formation

Summary From model roastings of mixtures containing serine, threonine and sucrose about 350 volatile compounds were separated and identified by GC/MS. Among them there were more than 100 monocyclic furans, 13 furanones and 8 bicyclic furans, the mass spectra and retention indices of which are recorded. The most important mass spectrometric fragmentation pathways are described. Spectra obtained from roasting coffee under identical conditions are compared with the spectra from model roastings.

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Modell-Reaktionen zur Röstaroma-BildungII. Die massenspektrometrische Identifizierung von Furanen und Furanonen aus der Reaktion von Serin und Threonin mit Saccharose unter den Bedingungen der Kaffeeröstung

Zusammenfassung Aus Modellröstungen von Gemischen aus Serin, Threonin und Saccharose unter den Bedingungen der Kaffeeröstung wurden etwa 350 flüchtige Verbindungen mittels GC/MS getrennt und identifiziert. Unter ihnen befanden sich über 100 monocyclische Furane und 13 Furanone sowie 8 bicyclische Furane, deren Massenspektren und Retentions-indices angegeben werden. Die wichtigsten massenspektrometrischen Fragmentierungswege werden beschrieben. -Die aus einer gleich behandelten Röstung von Rohkaffee erhaltenen Spektren werden mit denen der Modellröstungen verglichen.

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Dissertation Gloria Bochmann, TU Berlin 1984     

Segregation band formation in Al-Si die castings

Banded defects are often found in high-pressure die castings. These bands can contain segregation, porosity, and/or tears, and changing casting conditions and alloy are known to change the position and make-up of the bands. Due to the complex, dynamic nature of the high-pressure die-casting (HPDC) process, it is very difficult to study the effect of individual parameters on band formation. In the work presented here, bands of segregation similar to those found in cold-chamber HPDC aluminum alloys were found in laboratory gravity die castings. Samples were cast with a range of fraction solids from 0 to 0.3 and the effect of die temperature and external solid fraction on segregation bands was investigated. The results are considered with reference to the rheological properties of the filling semisolid metal and a formation mechanism for bands is proposed by considering flow past a solidifying immobile wall layer.     

Parabolic dish concentrators approximated by simple surfaces

Two different concentrating mirrors have been constructed that resemble parabolic dish reflectors. Both mirrors are made of slightly curved strips of flat, bendable material. The strips of the most simplified mirror have only large-radius circles and straight lines as boundaries. The necessary equations for making the mirrors are given. Also a simple way to make a stiff, lightweight frame and support for the mirror strips has been developed. Models of the mirrors have been built and successfully used for cooking and baking.     

Synthesis,Characterization, and Reactivity of Lanthanide Complexes with Bulky Silylallyl Ligands

The synthesis of new lanthanide allyl complexes of enhanced stability and solubility in saturated hydrocarbons based on silyl-substituted allyl ligands is reported. Thus the potassium salt K(CH₂CHCHSiMe₃) ( 1 ) reacts with YCl₃ in tetrahydrofuran to give the tris-allyl complex Y(CH₂CHCHSiMe₃)₃ ( 2 ), while K(CH₂CHCHSiMe₂^tBu) ( 3 ) affords Y(CH₂CHCHSiMe₂^tBu)₃(THF)_1.5 ( 4 ). Slow re-crystallization of 4 from light petroleum in the presence of tert-butylcyanide led to multiple insertion to give the sec-amido complex Y{NHC(^tBu)(CH)₃SiMe₂^tBu}₂{η₂-NHC(^tBu)CH=CHCH₂SiMe₂^tBu)CH(CHCHSiMe₂^tBu)C^tBuNH}(THF)·(CH₃CH(Me)(CH₂)₂CH₃) ( 5 ), which was crystallographically characterized. The reaction of ScCl₃(THF)₃ with two equivalents of Li{1,3-C₃H₃(SiMe₃)₂} in tetrahydrofuran gives the bis-allyl complex {1,3-C₃H₃(SiMe₃)₂}₂Sc(μ-Cl)₂Li(THF)₂ ( 6 ), while the analogous reaction of K{1,3-C₃H₃(SiMe₃)₂} ( 7 ) with either LaCl₃ or YCl₃ in tetrahydrofuran affords the bis-allyl complexes MCl{1,3-C₃H₃(SiMe₃)₂}₂(THF)_x (8, M = La, x = 1; 9, M = Y, x = 0). An attempt to prepare the similar neodymium complex gave the mono-allyl complex NdI₂{1,3-C₃H₃(SiMe₃)₂}(THF)_1.25 ( 10 ). The reactions of 8 and 9 with triisobutyl aluminum in benzene-d₆ show allyl exchange between lanthanide and aluminum. Complexes 8 , 9 , and 10 have been tested with a variety of activator systems as catalysts for the polymerization of 1,3-butadiene.