Synthesis of Allylarenes via Catalytic Decarboxylation of Allyl Benzoates

A catalyst system consisting of the palladium(0) complex Pd₂(dba)₃ and tri(p‐tolyl)phosphine was found to efficiently promote the decarboxylation of allyl benzoates with formation of allylarenes. This catalytic C O activation followed by extrusion of carbon dioxide and C C bond formation represents a sustainable alternative to traditional waste‐intensive cross‐couplings. The scope of the transformation includes allyl and cinnamyl esters of various ortho‐substituted benzoic acids. For particularly activated substrates, the palladium catalyst can optionally be replaced by an inexpensive nickel complex.

     

A Novel Buffering Technique for Aqueous Processing of Zinc Oxide Nanostructures and Interfaces,and Corresponding Improvement of Electrodeposited ZnO‐Cu2O Photovoltaics

A novel buffering method is presented to improve the stability of zinc oxide processed in aqueous solutions. By buffering the aqueous solution with a suitable quantity of sacrificial zinc species, the dissolution of functional zinc oxide structures and the formation of unwanted impurities can be prevented. The method is demonstrated for ZnO films and nanowires processed in aqueous solutions used for the selective etching of mesoporous anodic alumina templates and the electrochemical deposition of Cu₂O. In both cases, improved ZnO stability is observed with the buffering method. ZnO‐Cu₂O heterojunction solar cells (bilayer and nanowire cells) synthesized using both traditional and buffered deposition methods are characterized by impedance spectroscopy and solar simulation measurements. Buffering the Cu₂O deposition solution is found to reduce unwanted recombination at the heterojunction and improve the photovoltaic performance.     

An Innovative Approach to Tissue Processing and Cell Sorting of Fixed Cells for Subsequent Single-Cell RNA Sequencing

Although single-cell RNA sequencing (scRNA-seq) is currently the gold standard for the analysis of cell-specific expression profiles, the options for processing, staining, and preserving fresh cells remain very limited. Immediate and correct tissue processing is a critical determinant of scRNA-seq success. One major limitation is the restricted compatibility of fixation approaches, which must not destabilize or alter antibody labeling or RNA content or interfere with cell integrity. An additional limitation is the availability of expensive, high-demand cell-sorting equipment to exclude debris and dead or unwanted cells before proceeding with sample sequencing. The goal of this study was to develop a method that allows cells to be fixed and stored prior to FACS sorting for scRNA-seq without compromising the quality of the results. Finally, the challenge of preserving as many living cells as possible during tissue processing is another crucial issue addressed in this study. Our study focused on pancreatic ductal adenocarcinoma samples, where the number of live cells is rather limited, as in many other tumor tissues. Harsh tissue dissociation methods and sample preparation for analysis can negatively affect cell viability. Using the murine pancreatic cancer model Pan02, we evaluated the semi-automated mechanical/enzymatic digestion of solid tumors by gentleMACS Dissociator and compared it with mechanical dissociation of the same tissue. Moreover, we investigated a type of cell fixation that is successful in preserving cell RNA integrity yet compatible with FACS and subsequent scRNA-sequencing. Our protocol allows tissue to be dissociated and stained in one day and proceeds to cell sorting and scRNA-seq later, which is a great advantage for processing clinical patient material.     

Catalytically Doped Semiconductors for Chemical Gas Sensing: Aerogel‐Like Aluminum‐Containing Zinc Oxide Materials Prepared in the Gas Phase

Atmospheric contamination with organic compounds is undesired in industry and in society because of odor nuisance or potential toxicity. Resistive gas sensors made of semiconducting metal oxides are effective in the detection of gases even at low concentration. Major drawbacks are low selectivity and missing sensitivity toward a targeted compound. Acetaldehyde is selected due to its high relevance in chemical industry and its toxic character. Considering the similarity between gas‐sensing and heterogeneous catalysis (surface reactions, activity, selectivity), it is tempting to transfer concepts. A question of importance is how doping and the resulting change in electronic properties of a metal‐oxide support with semiconducting properties alters reactivity of the surfaces and the functionality in gas‐sensing and in heterogeneous catalysis. A gas‐phase synthesis method is employed for aerogel‐like zinc oxide materials with a defined content of aluminum (n‐doping), which were then used for the assembly of gas sensors. It is shown that only Al‐doped ZnO represents an effective sensor material that is sensitive down to very low concentrations (<350 ppb). The advance in properties relates to a catalytic effect for the doped semiconductor nanomaterial.     

On the calculation and representation of multicomponent systems

A data set was established to calculate the phase equilibria in the systems Si-Al-Zr-O-N and Si-Al-B-O-N. Complete phase diagrams of the quasibinary and quasiternary boundary systems, calculated by this data set, agree well with literature phase diagrams. To calculate equilibria of the multicomponent systems, Eriksson's program was modified to accept ionic species. The equilibria of some concentrations are plotted versus the temperature in phase amount diagrams.