Substitution lability of the perfluorinated Cp* ligand in Rh(i) complexes

Several cationic rhodium(I) complexes [Rh(COD)L2][C5(CF3)5] have been synthesized through substitution of the weakly bound [C5(CF3)5]− ligand from [Rh(COD)(C5(CF3)5)], further emphasizing its unique reactivity. Besides acetonitrile, pyridine derivatives with varying degrees of fluorination have been employed as ligands in order to investigate the influence of fluorination upon the binding affinity towards the resulting [Rh(COD)]+ fragment and the limit as to which the [C5(CF3)5]− ligand can be displaced. Furthermore, the newly synthesized compounds represent rare examples of rhodium complexes containing fluorinated pyridines as ligands

Tenfold Metalation of Ferrocene: Synthesis, Structures and Metallophilic Interactions in FeC10(HgX)10

The permercuration of ferrocene was achieved by reacting ferrocene with 10 equivalents of mercury(II) butyrate Hg(O2CC3H7)2 in a facile one‐pot reaction in multi‐gram scale and high yields. The butyrate groups in FeC10(HgX)10 (X=O2CC3H7) can be exchanged by treatment with trifluoro‐ or trichloroacetic acid (X=O2CCF3, O2CCCl3). Substitution of the trifluoroacetate groups by halides (X=Cl, F) proceeds easily in aqueous THF. The completeness of metalation was confirmed by NMR and vibrational spectroscopy, mass spectrometry, as well as elemental analysis. Additionally, the first crystal structures of permetallated metallocenes are presented: FeC10(HgX)10 (X=Cl, O2CCF3, O2CCCl3)

»Bemitleide dich mal nicht selbst!« : Reaktionsmuster auf Psychotherapieberichte über Patienten mit und ohne Gewalterfahrung

Gewalterfahrungen in der Kindheit und Jugend werden möglicherweise psychisch so verarbeitet, dass das Gegenüber später in einer spezifischen Weise auf die Betroffenen reagiert. Wir untersuchten dies anhand der Frage, ob sich Reaktionen (Assoziationen) auf Berichte an den Gutachter dahingehend unterscheiden, ob der Patient Gewalterfahrungen in der Kindheit oder Jugend in der Herkunftsfamilie gemacht hat oder nicht. Es wurden 22 pseudonymisierte Berichte an den Gutachter im Rahmen des Antragsverfahrens auf Kostenübernahme von Psychotherapie von zwei Untersucherinnen qualitativ analysiert. Die Analyse erfolgte über die Qualitative Inhaltsanalyse nach Mühlfeld. Beim Vergleich der deduktiv entwickelten Kategoriensysteme konnten im Hinblick auf die Reaktionsmuster Parallelen, aber auch mehrere Differenzen zwischen den beiden Patientengruppen festgestellt werden. Als Reaktionsmuster auf Patienten mit Gewalterfahrung zeigten sich Sprachlosigkeit, Tod oder Sich-verstecken-Wollen, was sich so bei der anderen Gruppe nicht fand. Parallelen ergaben sich unter anderem bei Reaktionsmustern von Zartheit, Ekel oder Relativierung von Leid. Bei Berichten über Patienten ohne Gewalterfahrung kam es zu einer größeren emotionalen Varianz in den Reaktionsmustern. Die gefundenen Reaktionsmuster stimmen nur teilweise mit Angaben der Literatur zu „typischen“ Gegenübertragungsreaktionen auf traumatisierte Patienten überein. Die geringere emotionale Varianz gegenüber Berichten von Patienten mit Gewalterfahrungen könnte ein empirischer Beleg für deren geringere Symbolisierungsfähigkeiten sein.Experiences with violence in childhood and adolescence are possibly mentally processed by the victim in such a way that other individuals later react in a particular manner towards the victim. We investigated this based on the question whether reactions (associations) towards the psychotherapy reports to the reviewer differ depending on whether the patients experienced violence in childhood and adolescence within their birth family or not. A qualitative analysis of 22 pseudonymized psychotherapy reports to the reviewer was performed by two investigators in the context of the application procedure for reimbursement of costs. The analysis was carried out using the qualitative content analysis according to Mühlfeld. By a comparison of the deductively developed category system, parallels but also several differences could be found between the two patient groups with respect to the reaction patterns. As reaction patterns to patients with experience of violence we found speechlessness, death or wanting to hide, which was not found in the other group. Similar reaction patterns between the two patient groups included tenderness, disgust and the relativization of suffering. A broader variance of emotions emerged in the reaction patterns when reading the psychotherapy reports of the patients without experience of violence. The reaction patterns found only partially matched the descriptions in the literature on “typical” countertransference reactions in the context of traumatized patients. The lower emotional variance to reports of patients with experience of violence could be empirical evidence of their lower capability for symbolization

Introducing the Perfluorinated Cp* Ligand into Coordination Chemistry

The reaction of AgBF4 and [Rh(COD)Cl]2 (COD=1,5-cyclooctadiene) in presence of [NEt4][C5(CF3)5] afforded the fluorocarbon soluble complex [Rh(COD)(C5(CF3)5)] by salt metathesis. This complex represents the first example for a successful coordination of the weakly basic [C5(CF3)5]− ligand, since its first synthesis in 1980. In addition to [Rh(COD)(C5(CF3)5)] also the byproduct [Rh(COD)(C5(CF3)4H)] was isolated and fully characterized. Accompanying DFT studies showed that the interaction energy of the [C5(CF3)5]− ligand towards the 12-electron fragment [Rh(COD)]+ is ≈70 kcal mol−1 lower in comparison to [C5(CH3)5]− due to reduced electrostatic interactions and weaker π-donor properties of the ligand. The quantitative but reversible substitution of the [C5(CF3)5]− ligand by toluene, converting it into a weakly coordinating anion, experimentally proved the extraordinary weak bonding interaction

What is considered to be emotional suffering by psychotherapy patients and their therapists in Eastern versus Western Germany? : A mixed-methods study

PURPOSE This study examined what aspects of life in Eastern and Western Germany are considered by patients, therapists and society to cause (or indicate) emotional suffering so that outpatient psychotherapy is sought and warranted. METHODS In Germany, psychotherapy is covered by health insurance after patients submit an application accompanied by a written report from the therapist. We took a random sample of such applications and performed a qualitative text analysis of the reports, identifying all text units where some form of emotional suffering, distress or handicap was described. A coding system was developed based on the units, and all units were subsequently coded. The proportion of units per category was compared between reports from Western and Eastern Germany using chi-square tests. RESULTS Out of 500 randomly selected reports, 25 were from Eastern Germany. An age- and sex-matched sample from Western Germany was added. From these 50 reports, a total of 716 text units describing some form of emotional suffering were extracted (359 units from reports from Eastern Germany and 357 from Western Germany). Thirteen categories of emotional suffering emerged. In Eastern Germany, emotional suffering was considerably more frequently described in terms of somatic symptoms and in feeling nervous and tense. Patients from Western Germany were more often described as feeling depressed and hopeless, helpless, anxious and without drive (ϕ = 0.19, p = .02). CONCLUSION There is evidence that there are differences between Eastern and Western Germany in how emotional suffering is expressed and/or described

Persilylation of ferrocene: the ultimate discipline in sterically overcrowded metal complexes

We report the preparation and structural characterization of the first persilylated metallocene via the metalation of decabromoferrocene. Although Grignard conditions turned out to be insufficient due to the steric and electronic effects of silyl groups causing a decreased nucleophilicity of the metalated intermediates, stepwise lithium–halogen exchange yields complex mixtures of polysilylated compounds FeC10DMSnH10−n (n = 10, 9, 8) including the targeted decasilylated ferrocene. These mixtures were successfully separated allowing a systematic study of silylation effects on ferrocene by XRD, CV, NMR and UV/vis spectroscopy supported by DFT calculations. The findings were used to develop a high-yielding and simple preparation method to generate a tenfold substituted overcrowded ferrocene, FeC10DMS8Me2

A Proteomic View of an Important Human Pathogen – Towards the Quantification of the Entire Staphylococcus aureus Proteome

The genome sequence is the “blue-print of life,” but proteomics provides the link to the actual physiology of living cells. Because of their low complexity bacteria are excellent model systems to identify the entire protein assembly of a living organism. Here we show that the majority of proteins expressed in growing and non-growing cells of the human pathogen Staphylococcus aureus can be identified and even quantified by a metabolic labeling proteomic approach. S. aureus has been selected as model for this proteomic study, because it poses a major risk to our health care system by combining high pathogenicity with an increasing frequency of multiple antibiotic resistance, thus requiring the development of new anti-staphylococcal therapy strategies. Since such strategies will likely have to target extracellular and surface-exposed virulence factors as well as staphylococcal survival and adaptation capabilities, we decided to combine four subproteomic fractions: cytosolic proteins, membrane-bound proteins, cell surface-associated and extracellular proteins, to comprehensively cover the entire proteome of S. aureus. This quantitative proteomics approach integrating data ranging from gene expression to subcellular localization in growing and non-growing cells is a proof of principle for whole-cell physiological proteomics that can now be extended to address physiological questions in infection-relevant settings. Importantly, with more than 1700 identified proteins (and 1450 quantified proteins) corresponding to a coverage of about three-quarters of the expressed proteins, our model study represents the most comprehensive quantification of a bacterial proteome reported to date. It thus paves the way towards a new level in understanding of cell physiology and pathophysiology of S. aureus and related pathogenic bacteria, opening new avenues for infection-related research on this crucial pathogen

Escherichia coli Can Adapt Its Protein Translocation Machinery for Enhanced Periplasmic Recombinant Protein Production

Recently, we engineered a tunable rhamnose promoter-based setup for the production of recombinant proteins in E. coli. This setup enabled us to show that being able to precisely set the production rate of a secretory recombinant protein is critical to enhance protein production yields in the periplasm. It is assumed that precisely setting the production rate of a secretory recombinant protein is required to harmonize its production rate with the protein translocation capacity of the cell. Here, using proteome analysis we show that enhancing periplasmic production of human Growth Hormone (hGH) using the tunable rhamnose promoter-based setup is accompanied by increased accumulation levels of at least three key players in protein translocation; the peripheral motor of the Sec-translocon (SecA), leader peptidase (LepB), and the cytoplasmic membrane protein integrase/chaperone (YidC). Thus, enhancing periplasmic hGH production leads to increased Sec-translocon capacity, increased capacity to cleave signal peptides from secretory proteins and an increased capacity of an alternative membrane protein biogenesis pathway, which frees up Sec-translocon capacity for protein secretion. When cells with enhanced periplasmic hGH production yields were harvested and subsequently cultured in the absence of inducer, SecA, LepB, and YidC levels went down again. This indicates that when using the tunable rhamnose-promoter system to enhance the production of a protein in the periplasm, E. coli can adapt its protein translocation machinery for enhanced recombinant protein production in the periplasm

Phenolic Substitution in Fidaxomicin: A Semisynthetic Approach to Antibiotic Activity Across Species

Fidaxomicin (Fdx) is a natural product antibiotic with potent activity against Clostridioides difficile and other Gram-positive bacteria such as Mycobacterium tuberculosis. Only a few Fdx derivatives have been synthesized and examined for their biological activity in the 50 years since its discovery. Fdx has a well-studied mechanism of action, namely inhibition of the bacterial RNA polymerase. Yet, the targeted organisms harbor different target protein sequences, which poses a challenge for the rational development of new semisynthetic Fdx derivatives. We introduced substituents on the two phenolic hydroxy groups of Fdx and evaluated the resulting trends in antibiotic activity against M. tuberculosis, C. difficile, and the Gram-negative model organism Caulobacter crescentus. As suggested by the target protein structures, we identified the preferable derivatisation site for each organism. The derivative ortho-methyl Fdx also exhibited activity against the Gram-negative C. crescentus wild type, a first for fidaxomicin antibiotics. These insights will guide the synthesis of next-generation fidaxomicin antibiotics