Putting aromatic compounds to work: Rational synthesis of organic 2D polymers

This contribution describes two different approaches aimed at the synthesis of monolayer molecular sheets with internal order, or, in other words, 2D polymers. First, an interfacial strategy is presented in which terpyridene-based hexafunctional monomers spread at the air/water interface are connected to one another with the help of metal salts. While this approach leads to micrometer-sized monolayer sheets that are mechanically stable enough to be spanned over several micrometer-sized holes, their internal structure could not yet be proven. The second approach rests upon solid-state photochemistry, and properly designed monomers are covalently connected with one another while being held in layered geometries owing to crystal packing. Exfoliation to single sheets can be achieved, and molecular structure is supported by a Raman spectroscopic analysis. We consider this the first case of a rational synthesis of 2D polymers and briefly touch on the impact this may hav

Scalable Synthesis of Two-dimensional Polymer Crystals and Exfoliation into Nanometer-thin Sheets

Two-dimensional materials have moved into the spotlight of researchers. The isolation of single graphene sheets has shown that restricted dimensionality can lead to interesting properties. Bottom-up synthesis of organic, covalently-bonded structures is, however, still challenging. In this publication we give a synopsis of a recently published monomer that is easily accessible and reversibly provides chiral two-dimensional polymer single crystals, which can be exfoliated into nanometer-thin sheets and show promise for applications in, for example, nonlinear optics and ultrathin membranes

Polymers Going Rigid, Thick, and Laterally Infinite

This short review article provides insight into the impact organic chemistry can have on state-of-the-art materials creation. Three cases were selected from the authors' laboratory, the first being 'Suzuki polycondensation', a powerful method with which innovative organic chemistry was successfully transferred to polymer synthesis and which meanwhile has even found technical scale application. The second describes the decoration of linear polymers with a dense layer of regular branch work. Though seemingly a rather esoteric enterprise, these decorations resulted in considerable property changes as compared to other linear polymers and, additionally, led to the discovery of novel properties. Consequently, this area which is commonly referred to as 'dendronized polymers' in a world-wide activity has been developed into a ripe research field, presently under exploration for possible technical application. Finally, an example still very much in its first tumbling steps was selected to give yet another perspective of the role of organic chemistry in a materials-oriented chemistry. It aims at the generation of ultrathin, yet internally strictly defined, sheet-like macromolecules for which a great future is foreseen, e.g. as a 2D platform for the systematic construction of 3D matter

Angular Correlations in Internal Pair Conversion of Aligned Heavy Nuclei

We calculate the spatial correlation of electrons and positrons emitted by internal pair conversion of Coulomb excited nuclei in heavy ion collisions. The alignment or polarization of the nucleus results in an anisotropic emission of the electron-positron pairs which is closely related to the anisotropic emission of $\gamma$-rays. However, the angular correlation in the case of internal pair conversion exhibits diverse patterns. This might be relevant when investigating atomic processes in heavy-ion collisions performed at the Coulomb barrier.Comment: 27 pages + 6 eps figures, uses revtex.sty and epsf.sty, tar-compressed and uuencoded with uufile

The impact of celestial pole offset modelling on VLBI UT1 Intensive results

Very Long Baseline Interferometry (VLBI) Intensive sessions are scheduled to provide operational Universal Time (UT1) determinations with low latency. UT1 estimates obtained from these observations heavily depend on the model of the celestial pole motion used during data processing. However, even the most accurate precession-nutation model, IAU 2000/2006, is not accurate enough to realize the full potential of VLBI observations. To achieve the highest possible accuracy in UT1 estimates, a celestial pole offset (CPO), which is the difference between the actual and modelled precession-nutation angles, should be applied. Three CPO models are currently available for users. In this paper, these models have been tested and the differences between UT1 estimates obtained with those models are investigated. It has been shown that neglecting CPO modelling during VLBI UT1 Intensive processing causes systematic errors in UT1 series of up to 20 microarcseconds. It has been also found that using different CPO models causes the differences in UT1 estimates reaching 10 microarcseconds. Obtained results are applicable to the satellite data processing as well.Comment: 8 pp., accepted for publication in Journal of Geodes

Topological analysis of polymeric melts: Chain length effects and fast-converging estimators for entanglement length

Primitive path analyses of entanglements are performed over a wide range of chain lengths for both bead spring and atomistic polyethylene polymer melts. Estimators for the entanglement length N_e which operate on results for a single chain length N are shown to produce systematic O(1/N) errors. The mathematical roots of these errors are identified as (a) treating chain ends as entanglements and (b) neglecting non-Gaussian corrections to chain and primitive path dimensions. The prefactors for the O(1/N) errors may be large; in general their magnitude depends both on the polymer model and the method used to obtain primitive paths. We propose, derive and test new estimators which eliminate these systematic errors using information obtainable from the variation of entanglement characteristics with chain length. The new estimators produce accurate results for N_e from marginally entangled systems. Formulas based on direct enumeration of entanglements appear to converge faster and are simpler to apply.Comment: Major revisions. Developed near-ideal estimators which operate on multiple chain lengths. Now test these on two very different model polymers

Inhibition or stimulation of ochratoxin a synthesis on inoculated barley triggered by diffuse coplanar surface barrier discharge plasma

Ochratoxin A (OTA) is one of the most abundant food-contaminating mycotoxins. Besides their high toxicity, mycotoxins are highly stable to physical, chemical or biological detoxification. Therefore, the treatment with cold atmospheric plasma could be one approach to reduce the amount of mycotoxins in different products. The aim of this study was to determine the influence of cold atmospheric plasma on the inactivation of Aspergillus niger and Penicillium verrucosum inoculated on barley and their production of OTA. Inoculated barley was treated with plasma generated by dry air, CO2 or CO2 + O2 for 1 or 3 min and stored for up to two weeks at 9, 25, or 37°C. Three minutes of air plasma treatment effectively significantly reduced the total mold count of both microorganisms by 2.5–3 log cycles. The production of OTA from A. niger was only low, therefore the treatment effect was indistinguishable. The treatment of P. verrucosum on barley after an incubation of five days using a CO2 + O2 plasma resulted in a reduction of the OTA content from 49.0 (untreated) to 27.5 (1 min) and 23.8 ng/g (3 min), respectively. In contrast, CO2 plasma caused an increase of the OTA amount from 49.0 (untreated) to 55.8 (1 min) and 72.9 ng/g (3 min). Finally, the use of air plasma resulted likewise in a decrease of the OTA concentration from 56.9 (untreated) to 25.7 (1 min) and 20.2 ng/g (3 min), respectively. Reducing the incubation time before the treatment to 24 h caused in contrast an increase of the OTA content from 3.1 (untreated) to 29.1 (1 min) and 20.7 ng/g (3 min). Due to the high standard deviation, these changes were not significant, but the tendencies were clearly visible, showing the strong impact of the plasma gas on the OTA production. The results show, that even if the total mold count was reduced, under certain conditions the OTA amount was yet enhanced, probably due to a stress reaction of the mold. Concluding, the plasma gas and incubation conditions have to be considered to allow a successful inactivation of molds and in particular their toxic metabolites

Screening of microbial communities associated with endive lettuce during postharvest processing on industrial scale

In this study, the composition of the microbial community on endive lettuce (Cichorium endivia) was evaluated during different postharvest processing steps. Microbial community structure was characterized by culture-dependent and culture-independent methods. Endive lettuce was sampled exemplarily at four different stages of processing (raw material, cut endive lettuce, washed endive lettuce, and spin-dried (ready to pack) endive lettuce) and analysed by plate count analysis using non-selective and selective agar plates with subsequent identification of bacteria colonies by matrix-assisted laser desorption/ionization time-of light mass spectrometry (MALDI-TOF MS). Additionally, terminal-restriction fragment length polymorphism (TRFLP) analysis and 16S rRNA gene nucleotide sequence analysis were conducted. The results revealed structural differences in the lettuce microbiomes during the different processing steps. The most predominant bacteria on endive lettuce were detected by almost all methods. Bacterial species belonging to the families Pseudomonadaceae, Enterobacteriaceae, Xanthomonadaceae, and Moraxellaceae were detected in most of the examined samples including some unexpected potentially human pathogenic bacteria, especially those with the potential to build resistance to antibiotics (e.g., Stenotrophomonas maltophilia (0.9 % in cut sample, 0.4 % in spin-dried sample), Acinetobacter sp. (0.6 % in raw material, 0.9 % in cut sample, 0.9 % in washed sample, 0.4 % in spin-dried sample), Morganella morganii (0.2 % in cut sample, 3 % in washed sample)) revealing the potential health risk for consumers. However, more seldom occurring bacterial species were detected in varying range by the different methods. In conclusion, the applied methods allow the determination of the microbiome's structure and its dynamic changes during postharvest processing in detail. Such a combined approach enables the implementation of tailored control strategies including hygienic design, innovative decontamination techniques, and appropriate storage conditions for improved product safety