When ferrocene and diiron organometallics meet: triiron vinyliminium complexes exhibit strong cytotoxicity and cancer cell selectivity

Cationic triiron complexes resulting from the conjugation of the ferrocenyl skeleton (Fc) with a diiron bis-cyclopentadienyl core through a variable vinyliminium linker, [Fe2Cp2(CO)(mu-CO){mu-eta(1):eta(3)-C(Fc)CHCN(R)(R')}]CF3SO3 ([2a-i]CF3SO3, Cp = eta(5)-C5H5, R, R'= alkyl, aryl), were synthesised in 70-94% yield, and the homologous nitrate salt was also prepared in one case ([2h]NO3). The neutral derivatives [Fe2Cp2(CO)(mu-CO){mu-eta(1):eta(3)-C(Fc)CHC(CN)NMe2}], 3, and [FeCp(CO){CN(Me)(Xyl)CHC(Fc)C(=O)}], 4 (Xyl = 2,6-C6H3Me2), were obtained in ca. 70% yield by reactions of the respective precursors [2h]CF3SO3 and [2i]CF3SO3 with NBu4CN and pyrrolidine, respectively. All products were purified by alumina chromatography and fully characterised by analytical and spectroscopic methods, and by single crystal X-ray diffraction in the cases of [2a]CF3SO3 and 3. The cytotoxicity of the complexes was assessed on A2780, A2780cisR and BxPC-3 cancer cell lines, and the nontumoral Balb/3T3 clone A31. Most of the cationic complexes display IC50 values in the low micromolar/nanomolar range concerning the cancer cell lines, and up to 35 times higher values on the nontumoral cells. In order to shed light on the mode of action, selected complexes were further characterised by cyclic voltammetry and spectroelectrochemical experiments, and assessed for their potential to trigger ROS production and to interact with a range of biomolecules, i.e. a synthetic dodecapeptide as a simplified model for thioredoxin reductase (TrxR-pept), some model proteins (cytochrome c, hen egg-white lysozyme, ubiquitin, bovine serum albumin, superoxide dismutase and human carbonic anhydrase) and one single-stranded oligonucleotide (ODN2)

Association of transportation noise with sleep during the first year of life: a longitudinal study

STUDY OBJECTIVES: During infancy, adequate sleep is crucial for physical and neurocognitive development. In adults and children, night-time noise exposure is associated with sleep disturbances. However, whether and to what extent infants' sleep is affected, is unknown. Thus, this study investigated the relationship between nocturnal transportation noise and actimetry-derived habitual sleep behavior across the first year of life. METHODS: In 144 healthy infants (63 girls), nocturnal (23:00-7:00) transportation noise (i.e., road, railway, and aircraft) was modelled at the infants' individual places of residence. Using actimetry, we recorded movement patterns for 11 days in a longitudinal design at 3, 6, and 12 months of age and derived the recently proposed core sleep composites of night-time sleep duration, activity, and variability. Using linear mixed-effects models, we determined associations between noise exposure and sleep composites. Sex, gestational age, parents' highest educational level, infants' age, and the existence of siblings served as control variables. RESULTS: In models without interactions, night-time transportation noise was unrelated to sleep composites across the first year of life (p > .16). Exploratory analyses of an interaction between noise and the existence of siblings yielded an association between night-time transportation noise and sleep duration in infants without siblings only (p = .004). CONCLUSION: In our study, sleep in infants during the first year of life was relatively robust against external perturbation by night-time transportation noise. However, particularly in children without siblings increasing night-time transportation noise reduced sleep duration. This suggests that the habitual noise environment may modulate individual susceptibility to adverse effects of noise on sleep

The Gerasimov-Drell-Hearn Sum Rule and the Spin Structure of the Nucleon

The Gerasimov-Drell-Hearn sum rule is one of several dispersive sum rules that connect the Compton scattering amplitudes to the inclusive photoproduction cross sections of the target under investigation. Being based on such universal principles as causality, unitarity, and gauge invariance, these sum rules provide a unique testing ground to study the internal degrees of freedom that hold the system together. The present article reviews these sum rules for the spin-dependent cross sections of the nucleon by presenting an overview of recent experiments and theoretical approaches. The generalization from real to virtual photons provides a microscope of variable resolution: At small virtuality of the photon, the data sample information about the long range phenomena, which are described by effective degrees of freedom (Goldstone bosons and collective resonances), whereas the primary degrees of freedom (quarks and gluons) become visible at the larger virtualities. Through a rich body of new data and several theoretical developments, a unified picture of virtual Compton scattering emerges, which ranges from coherent to incoherent processes, and from the generalized spin polarizabilities on the low-energy side to higher twist effects in deep inelastic lepton scattering.Comment: 32 pages, 19 figures, review articl

An active vesicle priming machinery suppresses axon regeneration upon adult CNS injury

Axons in the adult mammalian central nervous system fail to regenerate after spinal cord injury. Neurons lose their capacity to regenerate during development, but the intracellular processes underlying this loss are unclear. We found that critical components of the presynaptic active zone prevent axon regeneration in adult mice. Transcriptomic analysis combined with live-cell imaging revealed that adult primary sensory neurons downregulate molecular constituents of the synapse as they acquire the ability to rapidly grow their axons. Pharmacogenetic reduction of neuronal excitability stimulated axon regeneration after adult spinal cord injury. Genetic gain- and loss-of-function experiments uncovered that essential synaptic vesicle priming proteins of the presynaptic active zone, but not clostridial-toxin-sensitive VAMP-family SNARE proteins, inhibit axon regeneration. Systemic administration of Baclofen reduced voltage-dependent Ca2+ influx in primary sensory neurons and promoted their regeneration after spinal cord injury. These findings indicate that functional presynaptic active zones constitute a major barrier to axon regeneration

Scaling behavior of the spin pumping effect in ferromagnet/platinum bilayers

We systematically measured the DC voltage V_ISH induced by spin pumping together with the inverse spin Hall effect in ferromagnet/platinum bilayer films. In all our samples, comprising ferromagnetic 3d transition metals, Heusler compounds, ferrite spinel oxides, and magnetic semiconductors, V_ISH invariably has the same polarity. V_ISH furthermore scales with the magnetization precession cone angle with a universal prefactor, irrespective of the magnetic properties, the charge carrier transport mechanism or type. These findings quantitatively corroborate the present theoretical understanding of spin pumping in combination with the inverse spin Hall effect

Scaling behavior of the spin pumping effect in ferromagnet/platinum bilayers

We systematically measured the DC voltage V_ISH induced by spin pumping together with the inverse spin Hall effect in ferromagnet/platinum bilayer films. In all our samples, comprising ferromagnetic 3d transition metals, Heusler compounds, ferrite spinel oxides, and magnetic semiconductors, V_ISH invariably has the same polarity. V_ISH furthermore scales with the magnetization precession cone angle with a universal prefactor, irrespective of the magnetic properties, the charge carrier transport mechanism or type. These findings quantitatively corroborate the present theoretical understanding of spin pumping in combination with the inverse spin Hall effect

Gas Gain Uniformity Tests performed on Multi Wire Proportional Chambers for the LHCb Muon System

We present the experimental setup and the results of the gas gain uniformity tests performed as part of the quality control of the multiwire proportional chambers produced at CERN for the LHCb Muon system. The test provides a relative gas gain measurement over the whole chamber sensitive area. It is based on the analysis of the pulse height spectrum obtained when the chamber is exposed to {a^241}Am radioactive source. Since the measurement is normalized to the peak of a precise pulse generator, the gain uniformity can also be evaluated among different gas gaps and different chambers

Advanced resistivity model for arbitrary magnetization orientation applied to a series of compressive- to tensile-strained (Ga,Mn)As layers

The longitudinal and transverse resistivities of differently strained (Ga,Mn)As layers are theoretically and experimentally studied as a function of the magnetization orientation. The strain in the series of (Ga,Mn)As layers is gradually varied from compressive to tensile using (In,Ga)As templates with different In concentrations. Analytical expressions for the resistivities are derived from a series expansion of the resistivity tensor with respect to the direction cosines of the magnetization. In order to quantitatively model the experimental data, terms up to the fourth order have to be included. The expressions derived are generally valid for any single-crystalline cubic and tetragonal ferromagnet and apply to arbitrary surface orientations and current directions. The model phenomenologically incorporates the longitudinal and transverse anisotropic magnetoresistance as well as the anomalous Hall effect. The resistivity parameters obtained from a comparison between experiment and theory are found to systematically vary with the strain in the layer.Comment: 14 pages, 11 figures, submitted to Phys. Rev.