Looking on Heterogeneous Catalytic Systems from Different Perspectives: Multitechnique Approaches as a New Challenge for In Situ Studies

Adapting physico-chemical characterization techniques for in situ studies of real heterogeneous catalysts during conditioning, reaction, and deactivation processes is a research topic of growing importance. Up to now, in most studies only one single in situ technique is applied. However, new trends are focused on using a portfolio of several in situ methods to obtain comprehensive information on structure-reactivity relationships. This review discusses such application examples with the aim to point out the particular benefits that arise from multitechnique approaches for understanding processes like formation of active sites, interaction of those sites with reactant molecules, and catalyst deactivation. Except for Fourier-transform infrared spectroscopy and quasi-in situ X-ray photoelectron spectroscopy, the examples deal mainly with the combined use of bulk techniques such as electron paramagnetic resonance, ultraviolet/visible diffuse reflection spectroscopy, laser-Raman spectroscopy, temperature-programmed spectroscopy, X-ray diffraction, and X-ray absorption spectroscopy. However, although not being surface-sensitive per se, these techniques provide results relevant for the catalyzed reaction. Illustrative case studies comprise the investigation of (i) vanadia-based catalysts during selective oxidation and ammoxidation of toluene and during methanol synthesis, (ii) supported chromium oxides during octane aromatization, (iii) zeolite crystallization and catalysis, and (iv) a Cu/ZnO catalyst during methanol synthesis.     

Formal and relational governance in IT outsourcing: substitution,complementarity and the role of the psychological contract

This study aims to contribute to the literature on IT outsourcing governance by advancing our understanding of mechanisms of substitution and complementarity between formal and relational governance. Our study illustrates certain conditions under which substitution and complementarity can occur and depicts a two‐way causal relationship between them. Our examination further provides a more in‐depth assessment of relational governance by using the concept of the psychological contract. Our results demonstrate that the psychologically binding nature of the psychological contract makes it a particularly forceful substitute to formal governance, while its associations with other relationship aspects make it a forceful complement.     

Novel Azocoumarin Derivatives—Synthesis and Characterization

The paper presents synthesis and characterization of nine new thiazolyl-(phenyldiazenyl)-2H-chromen-2-one dyes. The impact of substituent structure in thiazole ring in the synthesized azocoumarin derivatives on electrochemical properties, photoisomerization process and photovoltaic response was examined. The dyes were electrochemically active and undergo reduction and oxidation processes. They showed low electrochemically estimated energy band gap in the range of 1.71–2.13 eV. Photoisomerization process of the synthesized molecules was studied in various solvents such as ethanol, chloroform and N,N-dimethylformamide (DMF) upon the UV illumination. It was found that novel azodyes showed reversible trans-cis-trans isomerization and exhibited long thermal back to the trans form, that was even 7 days in DMF. Selected azocoumarin were molecularly dispersed in polystyrene for preparation of guest-host azopolymer systems to study the cis-trans thermal isomerization of obtained dyes in solid state. The photovoltaic activity of the azochromophores was tested in bulk-heterojunction solar cells. They acting as weak donors in device with structure ITO/PEDOT:PSS/dye:PC70BM/Al. No photovoltaic response of cells with azocoumarin derivatives bearing 4-fluorobenzene, 3,4-dichlorobenzene, or 4-(1-adamantyl) unit was found. Additionally, dye which showed the best activity was examined in three-component solar cells ITO/PEDOT:PSS/PTB7:PC70BM:dye/PFN/Al.     

Eigenschaften und thermische Reaktionen von Komplexen der Arendiazoniumsalze mit Kronenethern

Properties and Thermal Reactions from Complexes of Arene Diazonium Salts with Crown Ethers In contrast to 18-crown-6, the substituted crown ethers Benzo-18-crown-6, Dibenzo-18-crown-6, and Naphtho-18-crown-6 form in solution complexes with p-CH₃ C₆H₄ N₂⁺BF₄-characterized by a broad charge transfer absorption up to 550 nm. The formation constants lg K_c are 2,32 2,16 and 1,44 for Benzo-, Dibenzo-, and Naphtho-18-crown-6, respectively. Formation enthalpy ΔH = −7,5 kJ/mol and entropy ΔS = +18 J/K mol are measured in the case of p-Cl C₆H₄ N₂⁺BF₄⁻ and Dibenzo-18-crown-6 (20°). K_c depends on substituents in the arene ring of the diazonium salt; ϱ = +0,8. Thermal dediazoniation in the presence of Crown ethers results in high yields of the corresponding arene. This is explained by a fast radical chain reaction between the diazonium salt and the polyether (Meerwein-Reduction).     

Characterisation of Trichomonas vaginalis Isolates Collected from Patients in Vienna between 2019 and 2021

Trichomonas vaginalis (TV) is the causative agent of trichomoniasis, the most common nonviral sexually transmitted disease. TV can carry symbionts such as Trichomonas vaginalis virus (TVV) or Mycoplasma hominis. Four distinct strains of TV are known: TVV1, TVV2, TVV3, and TVV4. The aim of the current study was to characterise TV isolates from Austrian patients for the presence of symbionts, and to determine their effect on metronidazole susceptibility and cytotoxicity against HeLa cells. We collected 82 TV isolates and detected presence of TVV (TVV1, TVV2, or TVV3) in 29 of them (35%); no TVV4 was detected. M. hominis was detected in vaginal/urethral swabs by culture in 37% of the TV-positive patients; M. hominis DNA was found in 28% of the TV isolates by PCR. In 15% of the patients, M. hominis was detected in the clinical samples as well as within the respective TV isolates. In 22% of the patients, M. hominis was detected by culture only. In 11 patients, M. hominis was detected only within the respective cultured TV isolates (13%), while the swab samples were negative for M. hominis. Our results provide a first insight into the distribution of symbionts in TV isolates from Austrian patients. We did not observe significant effects of the symbionts on metronidazole susceptibility, cytotoxicity, or severity of symptoms.     

Identification of Mitochondrial DNA (NUMTs) in the Nuclear Genome of Daphnia magna

This is the first study in which the Daphnia magna (D. magna) nuclear genome (nDNA) obtained from the GenBank database was analyzed for pseudogene sequences of mitochondrial origin. To date, there is no information about pseudogenes localized in D. magna genome. This study aimed to identify NUMTs, their length, homology, and location for potential use in evolutionary studies and to check whether their occurrence causes co-amplification during mitochondrial genome (mtDNA) analyses. Bioinformatic analysis showed 1909 fragments of the mtDNA of D. magna, of which 1630 were located in ten linkage groups (LG) of the nDNA. The best-matched NUMTs covering >90% of the gene sequence have been identified for two mt-tRNA genes, and they may be functional nuclear RNA molecules. Isolating the total DNA in mtDNA studies, co-amplification of nDNA fragments is unlikely in the case of amplification of the whole tRNA genes as well as fragments of other genes. It was observed that TRNA-MET fragments had the highest level of sequence homology, thus they could be evolutionarily the youngest. The lowest homology was found in the D-loop-derived pseudogene. It may probably be the oldest NUMT incorporated into the nDNA; however, further analysis is necessary.     

Assessment of Tailor-Made HPMC-Based Matrix Minitablets Comprising a Weakly Basic Drug Compound

Tailor-made, pH-controlled matrix minitablets based on different HPMC types were developed comprising the weakly basic drug dipyridamole. The incorporation of pH modifiers, i.e., fumaric and succinic acid, enhanced the drug release at pH 6.8. Assessing the drug release, acid release, and the microenvironmental pH (pH_M) provided detailed understanding of pH-controlled mini-matrices.

The extent and duration of pH_M alteration was more pronounced in presence of fumaric acid. Minitablets based on the fast dissolving Methocel K100LV (≤ 100 cps) showed simultaneous release rates of dipyridamole and fumaric acid with a constant low average pH_M.     

Substrate Templating upon Self‐Assembly of Hydrogen‐Bonded Molecular Networks on an Insulating Surface

Molecular self‐assembly on insulating surfaces, despite being highly relvant to many applications, generally suffers from the weak molecule–surface interactions present on dielectric surfaces, especially when benchmarked against metallic substrates. Therefore, to fully exploit the potential of molecular self‐assembly, increasing the influence of the substrate constitutes an essential prerequisite. Upon deposition of terephthalic acid and trimesic acid onto the natural cleavage plane of calcite, extended hydrogen‐bonded networks are formed, which wet the substrate. The observed structural complexity matches the variety realized on metal surfaces. A detailed analysis of the molecular structures observed on calcite reveals a significant influence of the underlying substrate, clearly indicating a substantial templating effect of the surface on the resulting molecular networks. This work demonstrates that choosing suitable molecule/substrate systems allows for tuning the balance between intermolecular and molecule–surface interactions even in the case of typically weakly interacting insulating surfaces. This study, thus, provides a strategy for deliberately exploiting substrate templating to increase the structural variety in molecular self‐assembly on a bulk insulator at room temperature.     

Isolation and characterization of a major allergen in kiwi fruit

 The isolation of an important allergen in kiwi fruit (Actinidia chinensis) by ion-exchange chromatography (IEC) and micropreparative SDS-PAGE followed by electroelution is reported. The purity of the allergen was analysed by SDS-PAGE and immunoblotting with sera from patients who have an allergy to kiwi. The allergen was shown to have a molecular weight of 43 kDa by SDS-PAGE/immunoblotting and an isoelectric point of approximately 6.9 as estimated by IEC. In accordance with World Health Organization nomenclature, this allergen is called Act c 2. By immunoblot inhibition it was shown that epitopes from different allergens in kiwi fruit are also located on Act c 2. N-terminal amino acid sequencing of 17 amino acid residues did not reveal homology with the major allergens in birch pollen (Bet v 1), apple (Mal d 1) or with other proteins of allergenic plant foods. In addition, the isoelectric point of a 67-kDa allergen in kiwi fruit was estimated to be 7.4 by IEC, but micropreparative isolation of this allergen failed because of its very low content in the fruit. Received: 14 April 1997