A Fully Integrated Continuous-Flow System for Asymmetric Catalysis: Enantioselective Hydrogenation with Supported Ionic Liquid Phase Catalysts Using Supercritical CO₂ as the Mobile Phase

A continuous-flow process based on a chiral transition-metal complex in a supported ionic liquid phase (SILP) with supercritical carbon dioxide (scCO2) as the mobile phase is presented for asymmetric catalytic transformations of low-volatility organic substrates at mild reaction temperatures. Enantioselectivity of >99 % ee and quantitative conversion were achieved in the hydrogenation of dimethylitaconate for up to 30 h, reaching turnover numbers beyond 100 000 for the chiral QUINAPHOS–rhodium complex. By using an automated high-pressure continuous-flow setup, the product was isolated in analytically pure form without the use of any organic co-solvent and with no detectable catalyst leaching. Phase-behaviour studies and high-pressure NMR spectroscopy assisted the localisation of optimum process parameters by quantification of substrate partitioning between the IL and scCO2. Fundamental insight into the molecular interactions of the metal complex, ionic liquid and the surface of the support in working SILP catalyst materials was gained by means of systematic variations, spectroscopic studies and labelling experiments. In concert, the obtained results provided a rationale for avoiding progressive long-term deactivation. The optimised system reached stable selectivities and productivities that correspond to 0.7 kg L−1 h−1 space–time yield and at least 100 kg product per gram of rhodium, thus making such processes attractive for larger-scale application

The Concept of Examining the Experiences of Deaf and Hard of Hearing Online Users

AbstractDespite the widespread popularity of social networking sites (SNSs) among the deaf and hard of hearing (D/HH), relatively little has been published about how to examine their experiences on SNSs in terms of creating online communities to support non-formal education, such as e-learning. With this regard, this paper sets forth a new approach and proposes a theoretical model for examining the experiences of D/HH users of SNSs from the aspects of identity, community building and alliances between communities. Factors, such as hearing loss, educational background, the communication situation and the use of technology are all considered with regard to their meaning for communication at SNSs. The main aim of the model is to examine experiences in informal online spaces and provide a set of guidelines for efficient social and communication support for D/HH online users at non-formal educational process which will in particular serve teachers, designers and developers included in the process. We also point to further research in order to implement the model in the field as well

Ligand Tuning in Pyridine-Alkoxide Ligated Cp*Ir III Oxidation Catalysts

Six novel derivatives of pyridine-alkoxide ligated Cp*IrIII complexes, potent precursors for homogeneous water and C–H oxidation catalysts, have been synthesized, characterized, and analyzed spectroscopically and kinetically for ligand effects. Variation of alkoxide and pyridine substituents was found to affect their solution speciation, activation behavior, and oxidation kinetics. Application of these precursors to catalytic C–H oxidation of ethyl benzenesulfonate with aqueous sodium periodate showed that the ligand substitution pattern, solution pH, and solvent all have pronounced influences on initial rates and final conversion values. Correlation with O2 evolution profiles during C–H oxidation catalysis showed these competing reactions to occur sequentially, and demonstrates how it is possible to tune the activity and selectivity of the active species through the N^O ligand structure

Behavioral problems of deaf and hard-of-hearing children. Secondary analysis of data from German studies using the SDQ-D

Es werden Ergebnisse einer Sekundäranalyse von 13 deutschsprachigen Studien zu Verhaltensauffälligkeiten bei hörgeschädigten Kindern (n = 1205) vorgestellt, die im Zeitraum zwischen 2001 und 2020 mit dem Strengths and Difficulties Questionnaire (SDQ-D) durchgeführt worden sind. Das Studienalter steht in keinem signifikanten Zusammenhang zur Häufigkeit von Verhaltensauffälligkeiten der untersuchten Kinder. Die Prävalenzdaten zeigen sowohl in der Einschätzung durch die Mütter als auch durch die Lehrkräfte im Vergleich zu hörenden Normierungsstichproben erhöhte Werte insbesondere in den Teilskalen „Verhaltensauffälligkeiten“ und „Probleme mit Gleichaltrigen“. Probleme mit Peers werden durch zahlreiche andere Studien in ihrer Bedeutung für die Entwicklung hörgeschädigter Kinder dokumentiert. Im Urteil der Mütter zeigen sich erhöhte Werte auch für die Teilskala „Emotionale Probleme“. Zusammenhangsanalysen mittels eines pfadanalytischen Vorgehens machen den Stellenwert der kommunikativen Kompetenz für die psychische Entwicklung sichtbar, während die Kommunikationsmodalität keine Rolle spielt. Dieser Befund wird in anderen Studien in vergleichbarer Weise dokumentiert. Ebenso werden Daten aus anderen Studien bestätigt, wonach Kinder, die eine zusätzliche Beeinträchtigung haben, und Kinder, die an einem Förderzentrum beschult werden, mehr Probleme in ihrer Entwicklung zeigen. Die Analyse der Subskalen des SDQ-D enthält Hinweise auf behinderungsspezifische Besonderheiten, die für die Förderung und die Gestaltung von Bildungsprozessen relevant sind. (DIPF/Orig.)Results of a reanalysis of 13 German studies on behavioral problems in deaf and hard-ofhearing (DHH) children (n = 1205) conducted between 2001 and 2020 using the Strengths and Difficulties Questionnaire (SDQ-D) are presented. Study age is not significantly related to the prevalence of behavioral problems in the children studied. Prevalence data show increased scores in both mothers’ and teachers’ assessments compared to hearing norming samples, particularly in the “behavioral problems” and “problems with peers” subscales. Problems with peers are documented by numerous other studies in their importance for the development of DHH children. The evaluation of the mothers also reveals increased scores regarding the subscale “emotional problems”. Additional analyses by means of a path analytic procedure indicate the importance of communicative competence for the psychological development, while the communication modality does not play a role. This result is documented in other studies in a comparable manner. Likewise, data from other studies confirm that DHH children who have an additional handicap and children who are educated at a school for the deaf and hard-of-hearing reveal more problems in their development. The analysis of the subscales of the SDQ-D indicate specific characteristics due to hearing loss that are relevant for educational promotion. (DIPF/Orig.

Social participation and quality of life of students deaf and hard-of-hearing in inclusive settings – the perspective of primary school teachers

In der vorliegenden Studie wird der Zusammenhang zwischen der sozialen Teilhabe einzelinklusiv beschulter hörgeschädigter Grundschüler/innen und deren Lebensqualität untersucht. Ebenso werden Prädiktoren der sozialen Teilhabe analysiert. Es liegen die Datensätze von 126 Schülern/innen im Alter zwischen sechs und zehn Jahren aus der Befragung von Grundschulpädagogen/innen vor. Beurteilt werden die soziale Teilhabe, die Lebensqualität, die sozialen und kommunikativen Kompetenzen und Verhaltensauffälligkeiten von hörgeschädigten Kindern. Die Einstellungen der befragten Lehrkräfte zur Inklusion werden ebenfalls erfasst. Die Ergebnisse zeigen, dass die soziale Teilhabe mit der Lebensqualität und den kindlichen Kompetenzen in einem signifikanten Zusammenhang steht, jedoch nicht mit den Einstellungen der Lehrkräfte zur Inklusion. Soziale und kommunikative Kompetenzen sowie Verhaltensauffälligkeiten erweisen sich als relevante Prädiktoren für die Partizipationschancen. Zusammen mit den kindlichen Verhaltensauffälligkeiten besitzen die Partizipationschancen direkte Vorhersagekraft für die Lebensqualität. (DIPF/Orig.)The present study investigates the relationship between social participation of deaf and hard-ofhearing (DHH) students from inclusive settings and their quality of life. Also, predictors of social participation are analyzed. Data of 126 DHH students aged between six and ten years are presented provided by the primary school teachers. There are measures available regarding social participation, quality of life, social and communicative skills and behavioral problems of the children. The attitudes of the teachers towards inclusion are also recorded. The results show that social participation is significantly related to quality of life and children‘s social-emotional and communicative competencies, but not to teachers‘ attitudes towards inclusion. Social and communicative competencies as well as behavioral problems prove to be a relevant predictor of social participation. Together with children’s behavioral problems, social participation has a direct effect for quality of life. (DIPF/Orig.

Online tracing of molecular weight evolution during radical polymerization via high-resolution FlowNMR spectroscopy

High-resolution FlowNMR was coupled to a continuous flow reactor to monitor polymer molecular weight evolution online by diffusion ordered NMR spectroscopy. Polymers were synthesized by reversible addition fragmentation chain transfer polymerization in continuous flow. The setup allows to target various polymer chain lengths in a dynamic manner without requiring additional purification or sample preparation. Obtaining molecular weight information in this manner is shown to be more accurate than classical SEC analysis at comparable measurement times, with relative errors around 5%

Importance of classroom listening conditions for the participation and quality of life of deaf and hard-of-hearing students in mainstream schools

Über 50 Prozent aller Kinder und Jugendlichen mit einem festgestellten sonderpädagogischen Förderbedarf im Bereich Hören (und Kommunikation) besuchen in Deutschland allgemeine Schulen. Da in inklusiven Bildungssettings vorwiegend in gesprochener Sprache kommuniziert wird, kann eine gute Hörqualität im Unterricht einen wichtigen Beitrag zur Sicherung der kommunikativen Partizipation und des Wohlbefindens der Schüler:innen leisten. Über die Zusammenhänge dieser drei Variablen ist bisher wenig bekannt. Der vorliegende Beitrag präsentiert die Ergebnisse einer Querschnittsuntersuchung, in der mittels standardisierter Fragebögen der Zusammenhang zwischen subjektiv beurteilter Hörqualität im Unterricht (E-HAK), kommunikativer Partizipation (CPQ-D) und Lebensqualität (KINDLR) untersucht wurde. Es liegen dazu die Daten von 156 Schüler:innen im Alter zwischen sieben und 18 Jahren vor. Die Ergebnisse der Korrelationsanalyse zeigen u. a. signifikante positive Zusammenhänge mit geringer bis mittlerer Effektstärke zwischen der subjektiv beurteilten Hörqualität im Unterricht und der kommunikativen Partizipation sowie zwischen der subjektiv beurteilten Hörqualität und der Lebensqualität. Subjektiv gut beurteilte Hörqualität ist mit einem besseren Verstehen der Äußerungen von Lehrkräften und Schüler:innen assoziiert und geht mit einer höher bewerteten Lebensqualität für den Bereich „Schule“ einher. Die Mediationsanalyse zeigt, dass der Zusammenhang von subjektiver Hörqualität und Lebensqualität durch die kommunikative Partizipation vermittelt wird. (DIPF/Orig.)Over 50 percent of all deaf and hard-of-hearing students in Germany attend mainstream schools. Since spoken language is the predominant means of communication in mainstream school classrooms, the listening conditions can substantially affect student participation and well-being in the classroom. However, little is known about the relationship between those three factors. This paper presents the results of a cross-sectional study using standardized questionnaires to investigate the relationship between subjective assessment of classroom listening quality (E-HAK), communicative participation (CPQ-D), and quality of life (KINDLR). Data from 156 pupils aged between 7 to 18 years were used. The results of the correlation analysis revealed significant positive correlations with low to medium effect sizes between subjective assessment of the listening quality and communicative participation and between the subjective assessment of listening quality and quality of life. In other words, a classroom environment assessed as having a good listening quality is associated both with better understanding of teachers and other pupils and with a higher-rated quality of life in school. A mediation analysis showed that communicative participation mediates the relationship between the subjectively assessed listening quality and the quality of life. (DIPF/Orig.

Unlocking the potential of supported liquid phase catalysts with supercritical fluids: low temperature continuous flow catalysis with integrated product separation

Solution-phase catalysis using molecular transition metal complexes is an extremely powerful tool for chemical synthesis and a key technology for sustainable manufacturing. However, as the reaction complexity and thermal sensitivity of the catalytic system increase, engineering challenges associated with product separation and catalyst recovery can override the value of the product. This persistent downstream issue often renders industrial exploitation of homogeneous catalysis uneconomical despite impressive batch performance of the catalyst. In this regard, continuous-flow systems that allow steady-state homogeneous turnover in a stationary liquid phase while at the same time effecting integrated product separation at mild process temperatures represent a particularly attractive scenario. While continuous-flow processing is a standard procedure for large volume manufacturing, capitalizing on its potential in the realm of the molecular complexity of organic synthesis is still an emerging area that requires innovative solutions. Here we highlight some recent developments which have succeeded in realizing such systems by the combination of near- and supercritical fluids with homogeneous catalysts in supported liquid phases. The cases discussed exemplify how all three levels of continuous-flow homogeneous catalysis (catalyst system, separation strategy, process scheme) must be matched to locate viable process conditions