ABSTRACT
INTRODUCTION: Research on leader-member exchange (LMX) has shown that the relation between leaders and followers may be considered from different angles. Leaders may form individual relationships with followers (LMX quality), may agree with their followers on these relationships (LMX agreement), and may form different relationships within their work group (LMX variability). We posit that leaders' mental health may function as an antecedent for these different forms of LMX. We use conservation-of-resources theory as a theoretical model to describe how leaders' mental health may interact with relationship quality with followers on different levels. METHODS: We operationalized leaders' mental health using depressive symptoms, anxiety, and stress reactivity. Our sample consisted of 322 followers of 75 leaders. Followers rated the LMX quality with their respective leader. Leaders rated depressive symptoms, anxiety, levels of stress reactivity, and LMX quality with their followers. RESULTS: Results of multilevel modeling showed that stress reactivity was negatively related to LMX quality and anxiety was positively linked to LMX agreement. Depressive symptoms were not related to aspects of LMX. CONCLUSION: By using multisource data on different analysis levels, we are able to include different perspectives on antecedents of LMX relationship quality. Implications for LMX at different levels of analysis as well as future research are discussed.
ABSTRACT
Octadentate and specifically nonadentate ligands with a bispidine scaffold (3,7-diazabicyclo[3.3.1]nonane) are known to be efficiently coordinated to a range of metal ions of interest in radiopharmaceutical chemistry and lead to exceedingly stable and inert complexes. Nonadentate bispidine L2 (with a tridentate bipyridine acetate appended to N3 and a picolinate at N7) has been shown before to be an ideal chelator for 111In3+, 177Lu3+, and 225Ac3+, nuclides of interest for diagnosis and therapy, and a proof-of-principle study with an SSTR2-specific octreotate has shown potential for theranostic applications. We now have extended these studies in two directions. First, we present ligand derivative L3, in which the bipyridine acetate is substituted with terpyridine, a softer donor for metal ions with a preference for more covalency. L3 did not fulfill the hopes because complexation is much less efficient. While for Bi3+ and Pb2+ the ligand is an excellent chelator with properties similar to those of L2, Lu3+ and La3+ show very slow and inefficient complexation with L3 in contrast to L2, and 225Ac3+ is not fully coordinated, even at an increased temperature (92% radiochemical yield at 80 °C, 60 min, [L3] = 10-4 M). These observations have led to a hypothesis for the complexation pathway that is in line with all of the experimental data and supported by a preliminary density functional theory analysis, which is important for the design of further optimized bispidine chelators. Second, the coordination chemistry of L2 has been extended to Bi3+, La3+, and Pb2+, including solid state and solution structural work, complex stabilities, radiolabeling, and radiostability studies. All complexes of this ligand (La3+, Ac3+, Lu3+, Bi3+, In3+, and Pb2+), including nuclides for targeted α therapy (TAT), single-photon emission computed tomography, and positron emission tomography, are formed efficiently under physiological conditions, i.e., suitable for the labeling of delicate biological vectors such as antibodies, and the complexes are very stable and inert. Importantly, for TAT with 225Ac, the daughter nuclides 213Bi and 209Pb also form stable complexes, and this is important for reducing damage to healthy tissue.
Subject(s)
Actinoid Series Elements , Lanthanoid Series Elements , Chelating Agents/chemistry , Radiopharmaceuticals/chemistry , Lanthanoid Series Elements/chemistry , Ligands , Lead , Ions/chemistry , AcetatesABSTRACT
EuIII , TbIII , GdIII and YbIII complexes of the nonadentate bispidine derivative L2 (bispidine=3,7-diazabicyclo[3.3.1]nonane) were successfully synthesized and their emission properties studied. The X-ray crystallography reveals full encapsulation by the nonadentate ligand L2 that enforces to all LnIII cations a common highly symmetrical capped square antiprismatic (CSAPR) coordination geometry (pseudo C4v symmetry). The well-resolved identical emission spectra in solid state and in solution confirm equal structures in both media. As therefore expected, this results in long-lived excited states and high emission quantum yields ([EuIII L2 ]+ , H2 O, 298â K, τ=1.51â ms, Ï=0.35; [TbIII L2 ]+ , H2 O, 298â K, τ=1.95â ms, Ï=0.68). Together with the very high kinetic and thermodynamic stabilities, these complexes are a possible basis for interesting biological probes.
Subject(s)
Lanthanoid Series Elements , Bridged Bicyclo Compounds, Heterocyclic , Ligands , LuminescenceABSTRACT
The nonheme iron(IV)-oxido complex trans-N3-[(L1 )FeIV =O(Cl)]+ , where L1 is a derivative of the tetradentate bispidine 2,4-di(pyridine-2-yl)-3,7-diazabicyclo[3.3.1]nonane-1-one, is known to have an S=1 electronic ground state and to be an extremely reactive oxidant for oxygen atom transfer (OAT) and hydrogen atom abstraction (HAA) processes. Here we show that, in spite of this ferryl oxidant having the "wrong" spin ground state, it is the most reactive nonheme iron model system known so far and of a similar order of reactivity as nonheme iron enzymes (C-H abstraction of cyclohexane, -90 °C (propionitrile), t1/2 =3.5â sec). Discussed are spectroscopic and kinetic data, supported by a DFT-based theoretical analysis, which indicate that substrate oxidation is significantly faster than self-decay processes due to an intramolecular demethylation pathway and formation of an oxido-bridged diiron(III) intermediate. It is also shown that the iron(III)-chlorido-hydroxido/cyclohexyl radical intermediate, resulting from C-H abstraction, selectively produces chlorocyclohexane in a rebound process. However, the life-time of the intermediate is so long that other reaction channels (known as cage escape) become important, and much of the C-H abstraction therefore is unproductive. In bulk reactions at ambient temperature and at longer time scales, there is formation of significant amounts of oxidation product - selectively of chlorocyclohexane - and it is shown that this originates from oxidation of the oxido-bridged diiron(III) resting state.
Subject(s)
Ferric Compounds , Iron , Bridged Bicyclo Compounds, Heterocyclic , Ligands , Oxidation-Reduction , OxygenABSTRACT
BACKGROUND: Mental illnesses have received increasing attention in the work context in recent years, yet they are still often accompanied by stigma. One starting point for stigma reduction is interventions in the workplace. The present study evaluated a one-day workshop for managers in a large company. METHOD: Enrolled managers (n = 70) were randomly assigned to the intervention group and the waiting control group. The training included a theoretical section on mental and stress-related diseases as well as the interplay between work and health, group work on personal stress experience, theoretical input on dealing with mentally ill employees, and a group discussion on this topic along with case studies. Both groups completed the following questionnaires at baseline and three months after training: Effort-Reward Imbalance Questionnaire, Patient Health Questionnaire, Mental Health Knowledge Schedule, Social Distance Scale, and the Irritation Scale. RESULTS: Compared to the waiting group, the intervention group showed a significant improvement in the Mental Health Knowledge Schedule (U = 417.00, p = 0.040) and an increase in the Irritation Scale (U = 371.50 p = 0.011). All other scales remained unchanged. CONCLUSION: The content and duration of the training were adequate to reduce cognitive stigma towards mental illness. However, the present approach was not sufficient for an improvement in the subjective stress level of the participating managers.
Subject(s)
Mental Disorders , Mental Health , Cognition , Humans , Mental Disorders/complications , Mental Disorders/therapy , Social Stigma , Workplace/psychologyABSTRACT
Squalamine lactate inhibits angiogenesis by a long-lived, intracellular mechanism of action. The drug is taken up into activated endothelial cells through caveolae, small invaginations in the cellular membrane. Subsequently, the drug binds to and "chaperones" calmodulin to an intracellular membrane compartment and blocks angiogenesis at several levels. A series of basic investigations, preclinical studies, and human clinical trials have begun to establish the proof of concept, efficacy, and safety parameters for use of squalamine lactate as a therapeutic agent for exudative age-related macular degeneration and several types of malignancies.
Subject(s)
Cholestanols/therapeutic use , Lactates/therapeutic use , Macular Degeneration/drug therapy , Animals , Exudates and Transudates , Humans , Treatment OutcomeABSTRACT
The interaction of Eu(III) and Cm(III) with three different aquatic fulvic acids (FA) was studied as a function of the temperature (T = 20-80 °C) in 0.1 M NaCl solution by time-resolved laser fluorescence spectroscopy. The speciation of both trivalent metal ions was determined by peak deconvolution of the recorded fluorescence spectra. For each studied metal ion-FA system only one complexed species is formed under the given experimental conditions. The stability constants at 20, 40, 60 and 80 °C (log ß'(T)) were determined according to the charge neutralization model. The log ß' (20 °C) for the different FAs show similar values (log ß(20 °C) = 5.60-6.29). The stability constants increase continuously with increasing temperature by approximately 0.3-1.0 orders of magnitude. The reaction enthalpies and entropies are derived from the integrated Van't Hoff equation. The results show that all investigated complexation reactions are endothermic and entropy-driven.
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OBJECTIVE: To evaluate the effects of combined vaginal and oral low-dose estrogen plus progestogen therapy (EPT) on the frequency and severity of dyspareunia, sexual function, and quality of life in recently postmenopausal women. METHODS: This outpatient, double-blind, randomized, placebo-controlled trial enrolled 285 healthy, sexually active postmenopausal women aged 45 to 65 years. Women received either one daily oral low-dose conjugated estrogens (0.45 mg)/medroxyprogesterone (1.5 mg) tablet for six 28-day cycles along with 1 g conjugated estrogens vaginal cream (0.625 mg), intravaginally for the first 6 weeks of the trial or a placebo cream and placebo tablet. Efficacy was evaluated using the McCoy Female Sexuality Questionnaire, self-reported daily diary cards, the Brief Index of Sexual Functioning-Women (BISF-W), and the Women's Health Questionnaire. RESULTS: The EPT group had a significant decrease in the frequency of dyspareunia compared with baseline and placebo in an analysis of responses to the McCoy Female Sexuality Questionnaire. Also, EPT was associated with a significant improvement in a woman's level of sexual interest, frequency of orgasm, and pleasure of orgasm. There was no effect of EPT use on coital frequency. The EPT group had significant improvement in receptivity/initiation and relationship satisfaction, although not in other BISF-W domains, versus placebo (BISF-W analysis) and significant improvement versus placebo on most Women's Health Questionnaire responses. CONCLUSIONS: EPT provided a statistically significant improvement compared with placebo in dyspareunia, sexual experience, and quality of life as measured in this study. In general, EPT also improved self-reported sexual perception and enjoyment significantly compared with placebo.