Low temperature magnetic properties of Nd2Ru2O7.

We present magnetic susceptibility, heat capacity, and neutron diffraction measurements of polycrystalline Nd2Ru2O7 down to 0.4 K. Three anomalies in the magnetic susceptibility measurements at 146, 21 and 1.8 K are associated with an antiferromagnetic ordering of the Ru4+ moments, a weak ferromagnetic signal attributed to a canting of the Ru4+ and Nd3+ moments, and a long-range-ordering of the Nd3+ moments, respectively. The long-range order of the Nd3+ moments was observed in all the measurements, indicating that the ground state of the compound is not a spin glass. The magnetic entropy of Rln2 accumulated up to 5 K, suggests the Nd3+ has a doublet ground state. Lattice distortions accompany the transitions, as revealed by neutron diffraction measurements, and in agreement with earlier synchrotron x-ray studies. The magnetic moment of the Nd3+ ion at 0.4 K is estimated to be 1.54(2)µ B and the magnetic structure is all-in all-out as determined by our neutron diffraction measurements.

Electrochemical initiation of electron-catalyzed phenanthridine synthesis by trifluoromethylation of isonitriles.

The electron-catalyzed formation of phenanthridines starting from isonitriles initiated by an electrochemical reduction of the Togni reagent is presented. The required number of faradays per mole of starting material and the respective yields clearly show the catalytic character of the electron in this reaction. The mechanism is supported by cyclic voltammetry experiments.

Intra- versus intermolecular electron transfer in radical nucleophilic aromatic substitution of dihalo(hetero)arenes - a tool for estimating π-conjugation in aromatic systems.

In this paper, the application of the double radical nucleophilic aromatic substitution (SRN1) in various dihalogenated, mostly diiodinated, π-conjugated systems as a tool for qualitatively estimating their π-conjugation is described. This approach uses electron delocalisation as a measure of π-conjugation. Electron injection into the π-system is achieved via reaction of an intermediate aryl radical, itself generated from a dihalogenated π-system via SET-reduction of the C-I bond and subsequent reaction with a thiolate anion. The generated arene radical anion can then further react with the second aryl-halogen moiety within the π-system via an intramolecular electron transfer process. The efficiency of this intramolecular electron transfer is related to the π-conjugation of the radical anion. If the π-conjugation within the aromatic unit is weak, the arene radical anion reacts via an intermolecular ET with the starting dihalide. The intramolecular ET process delivers a product of a double SRN1 substitution whereas the intermolecular ET pathway provides a product of a mono- SRN1 substitution. By simple product analysis of mono- versus double substitution, π-conjugation can be qualitatively evaluated. This mechanistic tool is applied to various dihalogenated π-conjugated systems and the results are discussed within the context of π-conjugation. The conjugation mode within the π-system and the length of the aromatic system are varied, and the effect of relative positioning of the two halides within small π-systems is also addressed.

Strong intermolecular antiferromagnetic verdazyl-verdazyl coupling in the solid state.

Strong magnetic couplings are generally observed intramolecularly in organic diradicals or in systems in which they are promoted by crystal engineering strategies involving, for example, transition metal ligation. We herein present a strong intermolecularly coupling verdazyl radical in the solid state without the use of such design strategies. The crystal structure of an acetylene-substituted verdazyl radical shows a unique antiparallel face-to-face orientation of the neighboring verdazyl molecules along with verdazyl-acetylene interactions giving rise to an alternating antiferromagnetic Heisenberg chain. Single crystal structural data at 80, 100, 173, and 223 K show that one of the π-stacking distances depends on temperature, while heat capacity data indicate the absence of a phase transition. Based on this structural input, broken symmetry DFT calculations predict a change from an alternating linear Heisenberg chain with two comparable coupling constants J1 and J2 at higher temperatures towards dominant pair interactions at lower temperatures. The predicted antiferromagnetic coupling is confirmed experimentally by magnetic susceptibility, solid-state EPR and NMR spectroscopic results.

Complex Field-Induced States in Linarite PbCuSO4(OH)2 with a Variety of High-Order Exotic Spin-Density Wave States.

Low-temperature neutron diffraction and NMR studies of field-induced phases in linarite are presented for magnetic fields H∥b axis. A two-step spin-flop transition is observed, as well as a transition transforming a helical magnetic ground state into an unusual magnetic phase with sine-wave-modulated moments ∥H. An effective J[over ˜]_{1}-J[over ˜]_{2} single-chain model with a magnetization-dependent frustration ratio α_{eff}=-J[over ˜]_{2}/J[over ˜]_{1} is proposed. The latter is governed by skew interchain couplings and shifted to the vicinity of the ferromagnetic critical point. It explains qualitatively the observation of a rich variety of exotic longitudinal collinear spin-density wave, SDW_{p}, states (9≥p≥2).

Determination of rate constants for trifluoromethyl radical addition to various alkenes via a practical method.

A simple and practical method for the determination of rate constants for trifluoromethyl radical addition to various alkenes by applying competition kinetics is introduced. In the kinetic experiments the trifluoromethyl radicals are generated in situ from a commercially available hypervalent-iodine-CF3 reagent (Togni-reagent) by SET-reduction with TEMPONa in the presence of TEMPO and a π-acceptor. From the relative ratio of TEMPOCF3 and CF3-addition product formed, which is readily determined by (19)F-NMR spectroscopy, rate constants for trifluoromethyl radical addition to the π-acceptor can be calculated. The practical method is also applicable to measure rate constants for the addition of other perfluoroalkyl radicals to alkenes as documented for CF3CF2-radical addition reactions.

An anatomic and morphometric analysis of splenic variability using 3D reconstruction and spatial orientation from computed tomography.

INTRODUCTION: In terms of frequency, the spleen is the first organ affected in abdominal trauma, resulting even today in a high rate of mortality (10%). Nevertheless, very few studies have investigated splenic quantitative morphometry as to shape and spatial orientation. Therefore, we analysed healthy spleen variability in order to integrate it in its environment and to correlate its morphometric parameters to anthropometric characteristics. METHODS: Ninety abdominopelvic CT-scans performed on patients over 16 years with no splenic pathology were retrospectively selected among a Mediterranean population. Three age groups ([16-30], [30-60] and [over 60 years]), equally distributed among genders, were created. Parameters, such as volume, characteristic checkpoints, orientation, and morphology, were measured on the spleen, the 11th thoracic vertebra and the 10th ribs in three-dimensional reconstructions. Anthropometric parameters were characterised by waist circumference, costo-xiphoid angle, abdominal height and chest depth. RESULTS: Observed variations in splenic morphology were divided into three groups: cupped (66.7%), coiled (17.8%), and flat (15.5%). Splenic morphometry tends to be abdominal-shaped (54.5%) or dorsal-shaped (45.5%). The mean of the angle between the main axis of the spleen and the CT-scan horizontal axis was 40±14°. Correlations were highlighted between volume and gender (p<0.05), splenic morphology and liver morphometry (p<0.05) as well as between orientation of hilar surface and splenic morphometry (p<0.01). Moreover, the spleen is more horizontal in women (p<0.05), in the elderly (p<0.05) and in the obese (p<0.01). CONCLUSION: This study defines three groups based on shape and highlights correlations between parameters describing healthy splenic variability and its anthropometric characteristics, which are of great importance for numerical modelling in splenic studies.

FeCr2S4 in magnetic fields: possible evidence for a multiferroic ground state.

We report on neutron diffraction, thermal expansion, magnetostriction, dielectric, and specific heat measurements on polycrystalline FeCr2S4 in external magnetic fields. The ferrimagnetic ordering temperatures TC ≈ 170 K and the transition at TOO ≈ 10 K, which has been associated with orbital ordering, are only weakly shifted in magnetic fields up to 9 T. The cubic lattice parameter is found to decrease when entering the state below TOO. The magnetic moments of the Cr- and Fe-ions are reduced from the spin-only values throughout the magnetically ordered regime, but approach the spin-only values for fields >5.5 T. Thermal expansion in magnetic fields and magnetostriction experiments indicate a contraction of the sample below about 60 K. Below TOO this contraction is followed by a moderate expansion of the sample for fields larger than ~4.5 T. The transition at TOO is accompanied by an anomaly in the dielectric constant. The dielectric constant depends on both the strength and orientation of the external magnetic field with respect to the applied electric field for T < TOO. A linear correlation of the magnetic-field-induced change of the dielectric constant and the magnetic-field dependent magnetization is observed. This behaviour is consistent with the existence of a ferroelectric polarization and a multiferroic ground state below 10 K.

Analysis of trait mean and variability versus temperature in trematode cercariae: is there scope for adaptation to global warming?

The potential of species for evolutionary adaptation in the context of global climate change has recently come under scrutiny. Estimates of phenotypic variation in biological traits may prove valuable for identifying species, or groups of species, with greater or lower potential for evolutionary adaptation, as this variation, when heritable, represents the basis for natural selection. Assuming that measures of trait variability reflect the evolutionary potential of these traits, we conducted an analysis across trematode species to determine the potential of these parasites as a group to adapt to increasing temperatures. Firstly, we assessed how the mean number of infective stages (cercariae) emerging from infected snail hosts as well as the survival and infectivity of cercariae are related to temperature. Secondly and importantly in the context of evolutionary potential, we assessed how coefficients of variation for these traits are related to temperature, in both cases controlling for other factors such as habitat, acclimatisation, latitude and type of target host. With increasing temperature, an optimum curve was found for mean output and mean infectivity, and a linear decrease for survival of cercariae. For coefficients of variation, temperature was only an important predictor in the case of cercarial output, where results indicated that there is, however, no evidence for limited trait variation at the higher temperature range. No directional trend was found for either variation of survival or infectivity. These results, characterising general patterns among trematodes, suggest that all three traits considered may have potential to change through adaptive evolution.

Driving magnetostructural transitions in layered intermetallic compounds.

We report the dramatic effect of applied pressure and magnetic field on the layered intermetallic compound Pr(0.5)Y(0.5)Mn(2)Ge(2). In the absence of pressure or magnetic field this compound displays interplanar ferromagnetism at room temperature and undergoes an isostructural first order magnetic transition (FOMT) to an antiferromagnetic state below 158 K, followed by another FOMT at 50 K due to the reemergence of ferromagnetism as praseodymium orders (T(C)(Pr)). The application of a magnetic field drives these two transitions towards each other, whereas the application of pressure drives them apart. Pressure also produces a giant magnetocaloric effect such that a threefold increase of the entropy change associated with the lower FOMT (at T(C)(Pr)) is seen under a pressure of 7.5 kbar. First principles calculations, using density functional theory, show that this remarkable magnetic behavior derives from the strong magnetoelastic coupling of the manganese layers in this compound.

Local effects of a global problem: modelling the risk of parasite-induced mortality in an intertidal trematode-amphipod system.

The interactive effects of climate change and parasitism are of concern because of potentially important consequences for host populations, communities and entire ecosystems. In marine environments, the absence of historic baseline data on parasitism and disease limits our ability to make realistic predictions about these consequences. Here, we adapt a simulation model developed for a Northern Hemisphere intertidal host-parasite system to a comparable system in the Southern Hemisphere. The entire life cycle of the intertidal trematode parasite Maritrema novaezealandensis was modelled in order to investigate the interactive effects of parasitic infections and increasing temperatures on the population dynamics of the amphipod host Paracalliope novizealandiae. Despite uncertainties associated with the model and its parameterisation, most temperature increases that were predicted to cause the collapse of the modelled amphipod population in the long term lay within the range of predicted warming for the study area. The high vulnerability of the amphipods in the modelled system illustrates a potentially important ecological mechanism by which consequences of a global problem might manifest on the local scale.

The magnetocaloric effect and critical behaviour of the Mn(0.94)Ti(0.06)CoGe alloy.

Structural, magnetic and magnetocaloric properties of the Mn(0.94)Ti(0.06)CoGe alloy have been investigated using x-ray diffraction, DC magnetization and neutron diffraction measurements. Two phase transitions have been detected, at T(str) = 235 K and T(C) = 270 K. A giant magnetocaloric effect has been obtained at around T(str) associated with a structural phase transition from the low temperature orthorhombic TiNiSi-type structure to the high temperature hexagonal Ni(2)In-type structure, which is confirmed by neutron study. In the vicinity of the structural transition, at T(str), the magnetic entropy change, -ΔS(M) reached a maximum value of 14.8 J kg(-1) K(-1) under a magnetic field of 5 T, which is much higher than that previously reported for the parent compound MnCoGe. To investigate the nature of the magnetic phase transition around T(C) = 270 K from the ferromagnetic to the paramagnetic state, we performed a detailed critical exponent study. The critical components γ, ß and δ determined using the Kouvel-Fisher method, the modified Arrott plot and the critical isotherm analysis agree well. The values deduced for the critical exponents are close to the theoretical prediction from the mean-field model, indicating that the magnetic interactions are long range. On the basis of these critical exponents, the magnetization, field and temperature data around T(C) collapse onto two curves obeying the single scaling equation M(H,ε) = Îµ(ß)f ± (H/ε(ß+γ)).

Cercarial survival in an intertidal trematode: a multifactorial experiment with temperature, salinity and ultraviolet radiation.

Parasite transmission takes place in the context of a multitude of simultaneously fluctuating environmental factors. As a particularly vulnerable step in the transmission, trematode cercariae are directly exposed to ambient conditions during their search for a host. Here, we investigated the survival of cercariae of the intertidal trematode Maritrema novaezealandensis in a multifactorial experiment (2 × 2 × 2 design) with temperature (20 and 30 °C), salinity (35 and 40 practical salinity units (psu)) and ultraviolet radiation (UVR; exposed and not exposed) as main factors. All factors had significant effects, with cercariae dying faster at the higher temperature, increased salinity and when exposed to UVR. Full activity ceased within ~6 h in all treatments at 30 °C, except at 35 psu under no exposure to UV; in all other treatments full activity was maintained for >6 h. Several factor interactions were identified, of which the interactive negative effect of temperature and UVR was the most important. These results imply that conditions during the main transmission window of M. novaezealandensis are highly challenging for cercariae. Our findings highlight the importance of considering multiple environmental factors in the study of parasite transmission to gain a more ecologically relevant understanding of transmission dynamics.

Effects of ultraviolet radiation on an intertidal trematode parasite: an assessment of damage and protection.

Trematode parasites are integral components of intertidal ecosystems which experience high levels of ultraviolet radiation. Although these parasites mostly live within hosts, their life cycle involves free-living larval transmission stages such as cercariae which are directly exposed to ambient conditions. UV has previously been shown to considerably reduce the survival of cercariae. Here, we investigated potential mechanisms of protection and damage related to UV in the intertidal trematode Maritrema novaezealandensis. Firstly, the presence of sunscreen compounds (i.e. mycosporine-like amino acids) was quantified in the parasite tissue producing cercariae within a snail host, as well as in the free-swimming cercariae themselves. Secondly, levels of oxidative stress in cercariae after exposure to UV were investigated (i.e.protein carbonyls, catalase and superoxide dismutase). Thirdly, the DNA damage (i.e. cyclobutane­pyrimidine dimers) was compared between cercariae exposed and not exposed to UV. Lastly, functional aspects(survival and infectivity) of cercariae were assessed, comparing cercariae under light conditions versus dark after exposure to UV. We confirmed the presence of my cosporine-like amino acids in cercariae-producing tissue from within snail hosts, but were unable to do so in cercariae directly. Results further suggested that exposure to UV induced high levels of oxidative stress in cercariae which was accompanied by a reduction in the levels of protective antioxidant enzymes present. We also identified higher levels of DNA damage in cercariae exposed to UV, compared with those not exposed. Moreover, no clear effect of light condition was found on survival and infectivity of cercariae after exposure to UV. We concluded that cercariae are highly susceptible to UV damage and that they have very little scope for protection against or repair of UV-induced damage.

Effects of ultraviolet radiation on the transmission process of an intertidal trematode parasite.

The transmission of parasites takes place under exposure to a range of fluctuating environmental factors, one being the changing levels of solar ultraviolet radiation (UVR). Here, we investigated the effects of ecologically relevant levels of UVR on the transmission of the intertidal trematode Maritrema novaezealandensis from its first intermediate snail host (Zeacumantus subcarinatus) to its second intermediate amphipod host (Paracalliope novizealandiae). We assessed the output of parasite transmission stages (cercariae) from infected snail hosts, the survival and infectivity of cercariae, the susceptibility of amphipod hosts to infection (laboratory experiments) and the survival of infected and uninfected amphipod hosts (outdoor experiment) when exposed to photo-synthetically active radiation only (PAR, 400-700 nm; no UV), PAR+UVA (320-700 nm) or PAR+UVA+UVB (280-700 nm). Survival of cercariae and susceptibility of amphipods to infection were the only two steps significantly affected by UVR. Survival of cercariae decreased strongly in a dose-dependent manner, while susceptibility of amphipods increased after exposure to UVR for a prolonged period. Exposure to UVR thus negatively affects both the parasite and its amphipod host, and should therefore be considered an influential component in parasite transmission and host-parasite interactions in intertidal ecosystems.

Integration and recording of a reconstituted voltage-gated sodium channel in planar lipid bilayers.

Functional assays for membrane proteins become increasingly important in biosciences. We demonstrate the integration of reconstituted bacterial voltage-gated sodium channels (NaChBac) into preformed free-standing lipid bilayers by using the nystatin-ergosterol method to promote proteoliposome fusion. Vesicle delivery and subsequent NaChBac activity were monitored, the orientation of the transferred ion channels was assessed measuring at both, positive and negative holding potentials and the channel specificity was demonstrated by adding the blocker nimodipine. A conductance of 120 pS per channel and an opening time in the range of seconds have been observed. Interestingly, we found that fusion of proteoliposomes into preformed free-standing bilayers is limited, if hydrophobically silanized silicon nitride membranes are used as the supporting material. In this case the diameter of the liposome had to be at least 20 times smaller compared to that of the pore to render fusion possible.

A technique for arthroscopic all-inside suturing in the wrist.

A technique for arthroscopic all-inside suturing in the wrist is presented. The procedure allows placement of the knot inside the joint without additional incisions. We have applied it in cases of dorsal, foveal and coronal tears of the triangular fibrocartilage. No special instrument is required apart from a Tuohy needle.

Progressive vestibular impairment in patients with polyneuropathy.

It is generally assumed that imbalance in patients with polyneuropathy (PNP) results from deficient proprioceptive input arriving from the lower limbs. Polyneuropathic processes, however, may also impair vestibular function. In fact, we observed that two-thirds of patients with PNP show unilateral or bilateral impairment of vestibular function as assessed with search-coil head impulse testing. In the present work, we analyzed the same database of 37 polyneuropathic patients to find out whether the presence of a unilateral or bilateral vestibular deficit reflects a progression of the vestibular impairment. Results suggest that vestibular function in PNP patients deteriorates asymmetrically, first affecting one side and later both sides.

Absence of estrogen receptor-related-alpha increases osteoblastic differentiation and cancellous bone mineral density.

The nuclear orphan receptor human estrogen receptor-related receptor (ERR)-alpha is implicated in bone metabolism. We studied the effect of ERRalpha silencing in human mesenchymal stem cells (hMSCs) during osteoblastogenesis. We found that ERRalpha silencing led to an increase of bone sialoprotein and a decrease of osteopontin mRNA levels, suggesting enhanced osteoblastic differentiation. This was confirmed by an increased ability of hMSCs to deposit calcium. Concomitantly, knockdown of ERRalpha inhibited adipogenesis, resulting in a decrease in adipocyte number and adipocyte marker gene expression. In line with a negative role of ERRalpha in bone metabolism, we found that adult female and male ERRalpha-deficient mice displayed a moderate increase in femoral cancellous bone volume and density. Osteoblast surface was increased and marrow fat volume decreased in these animals. Furthermore, ERRalpha-deficient osteoblasts displayed increased differentiation properties in vitro in line with our observations in hMSCs. In summary, we identified a role for ERRalpha in bone mass regulation by affecting osteoblastic differentiation.