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Die Verwendung von QR-Codes in Begleitseminaren zur Vorlesung „Organische Chemie“ für Studierende mit Chemie im Nebenfach wird vorgestellt. Die Hausaufgaben zu den Seminaren wurden mit einem QR-Code versehen. Dieser führt zu weiterführenden Hilfen. Der Einsatz der QR-Codes sowie die Neukonzeption der Seminare wurden evaluiert.
A new isoflavone, 8-prenylmilldrone (1), and four new rotenoids, oblarotenoids A-D (2-5), along with nine known compounds (6-14), were isolated from the CH2Cl2/CH3OH (1:1) extract of the leaves of Millettia oblata ssp. teitensis by chromatographic separation. The purified compounds were identified by NMR spectroscopic and mass spectrometric analyses, whereas the absolute configurations of the rotenoids were established on the basis of chiroptical data and in some cases by single-crystal X-ray crystallography. Maximaisoflavone J (11) and oblarotenoid C (4) showed weak activity against the human breast cancer cell line MDA-MB-231 with IC50 values of 33.3 and 93.8 mu M, respectively.
Quantum chemical approach to atomic manipulation of chlorobenzene on the Si(111)-7 x 7 surface
(2017)
We present a cluster model to describe the localization of hot charge carriers on the Si(111)-7 x 7 surface, which leads to (nonlocal) desorption of chlorobenzene molecules in scanning tunneling microscope (STM) manipulation experiments. The localized charge carriers are modeled by a small cluster. By means of quantum chemical calculations, this cluster model explains many experimental findings from STM manipulation. We show that the negative charge is mainly localized in the surface, while the positive one also resides on the molecule. Both resonances boost desorption: In the negative resonance the adatom is elevated; in the positive one the chemisorption bond between the silicon surface adatom and chlorobenzene is broken. We find normal modes promoting desorption matching experimental low-temperature activation energies for electron-and hole-induced desorption.
Quality attributes of fruit determine its acceptability by the retailer and consumer. The objective of this work was to investigate the potential of absorption (μa) and reduced scattering (μs’) coefficients of European pear to analyze its fruit flesh firmness and soluble solids content (SSC). The absolute reference values, μa* (cm−1) and μs’* (cm−1), of pear were invasively measured, employing multi-spectral photon density wave (PDW) spectroscopy at preselected wavelengths of 515, 690, and 940 nm considering two batches of unripe and overripe fruit. On eight measuring dates during fruit development, μa and μs’ were analyzed non-destructively by means of laser light backscattering imaging (LLBI) at similar wavelengths of 532, 660, and 830 nm by means of fitting according to Farrell’s diffusion theory, using fix reference values of either μa* or μs’*. Both, the μa* and the μa as well as μs’* and μs’ showed similar trends. Considering the non-destructively measured data during fruit development, μa at 660 nm decreased 91 till 141 days after full bloom (dafb) from 1.49 cm−1 to 0.74 cm−1 due to chlorophyll degradation. At 830 nm, μa only slightly decreased from 0.41 cm−1 to 0.35 cm−1. The μs’ at all wavelengths revealed a decreasing trend as the fruit developed. The difference measured at 532 nm was most pronounced decreasing from 24 cm−1 to 10 cm−1, while at 660 nm and 830 nm values decreased from 15 cm−1 to 13 cm−1 and from 10 cm−1 to 8 cm−1, respectively. When building calibration models with partial least-squares regression analysis on the optical properties for non-destructive analysis of the fruit SSC, μa at 532 nm and 830 nm resulted in a correlation coefficient of R = 0.66, however, showing high measuring uncertainty. The combination of all three wavelengths gave an enhanced, encouraging R = 0.89 for firmness analysis using μs’ in the freshly picked fruit.
Porous silicon single layer (PSM), bilayer (PSB) and pillar (PSP) structures have been evaluated as nucleation centers for vanadium pentoxide (V2O5) crystals. Deposition of vanadium precursor over different substrates (drop casting technique), followed by annealing treatment under Ar-H-2 (5% H-2) atmosphere, induced crystallization of vanadium oxide. With respect to c-Si/SiO2 substrate, V2O5 nanorods with relatively large aspect ratio were formed over and within PSP structures. On the other hand, pores in PSM and PSB were found to be filled with relatively smaller crystals. Additionally, PSB provided a nucleation substrate capable to align the nanocrystals in a preferential orientation, while V2O5 crystals grown on PSP were found to be randomly aligned around the nanoporous pillar microstructure. Nanorods and nanocrystals were identified as V2O5 by temperature-controlled XRD measurements and evidence of their crystalline nature was observed via transmission electron microscopy. A careful analysis of electronic microscopy images allows the identification of the facets composing the ends of the crystals and its corresponding surface free energy has been evaluated employing the Wulff theorem. Such high surface area composite structures have potential applications as cathode material in Lithium-ion batteries.
2-Deoxy-D-ribose-5-phosphate aldolase (DERA) is a biocatalyst that is capable of converting acetaldehyde and a second aldehyde as acceptor into enantiomerically pure mono- and diyhydroxyaldehydes, which are important structural motifs in a number of pharmaceutically active compounds. However, substrate as well as product inhibition requires a more-sophisticated process design for the synthesis of these motifs. One way to do so is to the couple aldehyde conversion with transport processes, which, in turn, would require an immobilization of the enzyme within a thin film that can be deposited on a membrane support. Consequently, we developed a fabrication process for such films that is based on the formation of DERA-poly(N-isopropylacrylamide) conjugates that are subsequently allowed to self-assemble at an air-water interface to yield the respective film. In this contribution, we discuss the conjugation conditions, investigate the interfacial properties of the conjugates, and, finally, demonstrate a successful film formation under the preservation of enzymatic activity.
Polyplexes between a double-stranded Salmon DNA and hyperbranched poly(ethyleneimine) (PEI) as well as a maltosylated PEI-Mal were incorporated into a gelatin/chitosan hydrogel scaffold. Calorimetric experiments of the polyplexes show a decrease of the melting temperature in presence of PEI and a peak splitting in presence of PEI-Mal, which can be interpreted to a partial compaction of the DNA strands in presence of PEI-Mal. When the polyplexes are incorporated into a gelatin/chitosan scaffold in the swollen state, the DNA melting peaks at 90 and 93 degrees C, respectively, indicate in both cases the release of the DNA at the surface of the hydrogel scaffold in a more compact form. Specific interactions between the PEI-Mal shell and gelatin are responsible for the tuning of the release properties in presence of the maltose units in the hyperbranched PEI.
Water deficit (drought stress) massively restricts plant growth and the yield of crops; reducing the deleterious effects of drought is therefore of high agricultural relevance. Drought triggers diverse cellular processes including the inhibition of photosynthesis, the accumulation of cell-damaging reactive oxygen species and gene expression reprogramming, besides others. Transcription factors (TF) are central regulators of transcriptional reprogramming and expression of many TF genes is affected by drought, including members of the NAC family. Here, we identify the NAC factor JUNGBRUNNEN1 (JUB1) as a regulator of drought tolerance in tomato (Solanum lycopersicum). Expression of tomato JUB1 (SlJUB1) is enhanced by various abiotic stresses, including drought. Inhibiting SlJUB1 by virus-induced gene silencing drastically lowers drought tolerance concomitant with an increase in ion leakage, an elevation of hydrogen peroxide (H2O2) levels and a decrease in the expression of various drought-responsive genes. In contrast, overexpression of AtJUB1 from Arabidopsis thaliana increases drought tolerance in tomato, alongside with a higher relative leaf water content during drought and reduced H2O2 levels. AtJUB1 was previously shown to stimulate expression of DREB2A, a TF involved in drought responses, and of the DELLA genes GAI and RGL1. We show here that SlJUB1 similarly controls the expression of the tomato orthologs SlDREB1, SlDREB2 and SlDELLA. Furthermore, AtJUB1 directly binds to the promoters of SlDREB1, SlDREB2 and SlDELLA in tomato. Our study highlights JUB1 as a transcriptional regulator of drought tolerance and suggests considerable conservation of the abiotic stress-related gene regulatory networks controlled by this NAC factor between Arabidopsis and tomato.
Potato (Solanum tuberosum L.) is one of the most important food crops worldwide. Current potato varieties are highly susceptible to drought stress. In view of global climate change, selection of cultivars with improved drought tolerance and high yield potential is of paramount importance. Drought tolerance breeding of potato is currently based on direct selection according to yield and phenotypic traits and requires multiple trials under drought conditions. Marker-assisted selection (MAS) is cheaper, faster and reduces classification errors caused by noncontrolled environmental effects. We analysed 31 potato cultivars grown under optimal and reduced water supply in six independent field trials. Drought tolerance was determined as tuber starch yield. Leaf samples from young plants were screened for preselected transcript and nontargeted metabolite abundance using qRT-PCR and GC-MS profiling, respectively. Transcript marker candidates were selected from a published RNA-Seq data set. A Random Forest machine learning approach extracted metabolite and transcript markers for drought tolerance prediction with low error rates of 6% and 9%, respectively. Moreover, by combining transcript and metabolite markers, the prediction error was reduced to 4.3%. Feature selection from Random Forest models allowed model minimization, yielding a minimal combination of only 20 metabolite and transcript markers that were successfully tested for their reproducibility in 16 independent agronomic field trials. We demonstrate that a minimum combination of transcript and metabolite markers sampled at early cultivation stages predicts potato yield stability under drought largely independent of seasonal and regional agronomic conditions.
Noninvasive imaging in the root soil compartment is mandatory for improving knowledge about root soil interactions and uptake processes which eventually control crop growth and productivity. Here we propose a method of MRI T-1 relaxation mapping to investigate water uptake patterns, and as second example, in combination with neutron tomography (NT), property changes in the rhizosphere. The first part demonstrates quantification of solute enrichment by advective transport to the roots due to water uptake. This accumulation is counterbalanced by net downward flow and dispersive spreading. One can furthermore discriminate between zones of high accumulation patterns and zones with much less enrichment. This behavior persists over days. The second part presents the novel combination of MRI with neutron tomography to couple static, proton density information of roots and their interface to the surrounding soil with information about the local water dynamics, reflected by NMR relaxation times. The root soil interface of a broad bean plant is characterized by slightly increasing MRI and NT signal intensity but decreasing T-1 relaxation time indicating locally changed soil properties.