Thiadiazolo-Azaacenes

This work reports the synthesis and characterization of bis- and tetrakis(thiadiazolo)-appended di- and tetraazaacenes, displaying up to seven catenated benzene/pyrazine rings. The targets are obtained by condensation of benzo-bis(thiadiazole)-4,5-dione with aromatic di- and tetraamines. The condensation products—up to a heptacene-like species—are stable but can be insoluble. Soluble derivatives are readily processible, but do not show enhanced electron affinities, as the two or four attached benzothiadiazole units are effectively resonance-separated from the acene body, maximizing the number of Clar-sextets.     

Speciation of gadolinium in surface water samples and plants by hydrophilic interaction chromatography hyphenated with inductively coupled plasma mass spectrometry

Hydrophilic interaction chromatography (HILIC) coupled with inductively coupled plasma mass spectrometry (ICP-MS) was optimized for speciation analysis of gadolinium-based contrast agents in environmental samples, in particular surface river waters and plants. Surface water samples from the Teltow channel, near Berlin, were investigated over a distance of 5 km downstream from the influx of a wastewater treatment plant. The total concentration of gadolinium increased significantly from 50 to 990 ng?L^?1 due to the influx of the contrast agents. After complete mixing with the river water, the concentration remained constant over a distance of at least 4 km. Two main substances [Dotarem® (Gd-DOTA) and Gadovist® (Gd-BT-DO3A)] have been identified in the river water using standards. A gadolinium-based contrast agent, possibly Gd-DOTA (Dotarem®), was also detected in water plant samples taken from the Teltow channel. Therefore, uptake of contrast agents [Gadovist® (Gd-BTDO3A), Magnevist® (Gd-DTPA), Omniscan® (Gd-DTPA-BMA), Dotarem® (Gd-DOTA), and Multihance® (Gd-BOPTA)] by plants was investigated in a model experiment using Lepidium sativum (cress plants). HILIC–ICP-MS was used for identification of different contrast agents, and a first approach for quantification using aqueous standard solutions was tested. For speciation analysis, all investigated contrast agents could be extracted from the plant tissues with a recovery of about 54 % for Multihance® (Gd-BOPTA) up to 106 % for Gadovist® (Gd-BT-DO3A). These experiments demonstrate that all contrast agents investigated are transported from the roots to the leaves where the highest content was measured.     

Regioselective Synthesis of Trichloromethyl‐Substituted Salicylates and Cyclohexenones by One‐Pot Cyclizations of 1,3‐Bis(trimethylsilyloxy)buta‐1,3‐dienes

A variety of 6‐(trichloromethyl)salicylates (=2‐hydroxy‐6‐(trichloromethyl)benzoates) were prepared by TiCl₄‐mediated cyclization of 1,3‐bis(trimethylsilyloxy)buta‐1,3‐dienes with 1,1,1‐trichloro‐4,4‐dimethoxybut‐3‐en‐2‐one. The employment of trimethylsilyl trifluoromethanesulfonate (Me₃SiOTf) as Lewis acid resulted in the formation of trichloromethyl‐substituted cyclohexenones. The cyclizations proceeded with good‐to‐very‐good regioselectivities.     

Determination of the total purity of a high-purity silver material to be used as a primary standard for element determination

A candidate material for the use as primary standard for silver determination was characterized with respect to total purity. Except the radioactive elements and He, all possible impurities were considered. Based on glow discharge mass spectrometry, inductively coupled plasma-mass spectrometry and carrier gas hot extraction measurements, the demonstrated total purity and its standard uncertainty is w(Ag) = (99.999 52 ± 0.000 11) %. The purity value and its uncertainty is dominated by the contributions from the measurements of the nonmetallic impurities, namely S, N, C and O.     

Hot Branching Dynamics in a Light‐Harvesting Iron Carbene Complex Revealed by Ultrafast X‐ray Emission Spectroscopy

Iron N‐heterocyclic carbene (NHC) complexes have received a great deal of attention recently because of their growing potential as light sensitizers or photocatalysts. We present a sub‐ps X‐ray spectroscopy study of an Fe^IINHC complex that identifies and quantifies the states involved in the deactivation cascade after light absorption. Excited molecules relax back to the ground state along two pathways: After population of a hot ³MLCT state, from the initially excited ¹MLCT state, 30 % of the molecules undergo ultrafast (150 fs) relaxation to the ³MC state, in competition with vibrational relaxation and cooling to the relaxed ³MLCT state. The relaxed ³MLCT state then decays much more slowly (7.6 ps) to the ³MC state. The ³MC state is rapidly (2.2 ps) deactivated to the ground state. The ⁵MC state is not involved in the deactivation pathway. The ultrafast partial deactivation of the ³MLCT state constitutes a loss channel from the point of view of photochemical efficiency and highlights the necessity to screen transition‐metal complexes for similar ultrafast decays to optimize photochemical performance.     

The role of metacognitive monitoring in explaining differences in mathematics achievement

The relationship between practised monitoring activities and performance, especially in mathematics was examined within three nested studies. The first study deals with problems of faulty term rewritings submitted to three groups of subjects—10th to 13th graders, differing in their mathematical performance—whose task was to find the mistakes. Moreover, a questionnaire on the practice and appreciation of monitoring activities was developed. The third study, first, repeats the first study with a similar population and secondly adds interviews with some of the subjects while solving additional items concerning faulty term rewritings. Studies 1 and 3 show similar success in finding mistakes and in the replies to the questionnaire within the various groups. Furthermore, the third study points up that the subject’s answers do neither predict the practised monitoring nor the success in the test. However, the success correlates significantly with the practised monitoring. For a deeper understanding concerning the role of metacognition in explaining performance, the second study examined two of the groups who had already been involved in the first study. These were assigned some problems of a matrices test as used in cognitive psychology. While trying to solve the problem, their eye movements were recorded by means of an eye-tracker. Afterwards they had to justify their solutions in an interview. The eye movements were analysed, the verbal comments classified. Again, the groups differ in their problem solving success, dependant on the quality of the monitoring practised. Altogether, the results of the three studies elucidate the importance of practised metacognitive monitoring activities not only for success in school algebra, but furthermore the ability and the willingness to do it is deeper anchored in a person than just a trained behaviour for school algebra.