Incommensurate magnetic ordering in CrB2.

Incommensurate magnetism in CrB2is studied in terms of a spin model based on density functional theory calculations. Heisenberg exchange interactions derived from the paramagnetic phase using the disordered local moment (DLM) theory show significant differences compared with those resulting from the treatment of the material as a ferromagnet; of these two methods, the DLM theory is found to give a significantly more realistic description. We calculate strongly ferromagnetic interactions between Cr planes but largely frustrated interactions within Cr planes. Although we find that the ground state ordering vector is sensitive to exchange interactions over a large number of neighbour shells, theq-vector of the incommensurate spin spiral state is satisfactorily reproduced by the theory (0.213 compared with the known ordering vector0.285×(2π)/(a/2)along Γ-K). The strong geometric frustration of the exchange interactions causes a rather low Néel temperature (about 97 K), also in good agreement with experiment.

Microstructuration of poly(3-hexylthiophene) leads to bifunctional superhydrophobic and photoreactive surfaces.

In this paper, we present the first report on an organic conducting polymer film, which alone exhibits both superhydrophobicity and visible light photoactivity. The microstructure of poly(3-hexylthiophene) was optimized using controlled precipitation until superhydrophobic behavior was achieved. Photocatalytic tests employing visible light irradiation proved that polymer degrades the ethanol test molecule.

Detecting patchy nanoparticle assembly at the single-particle level.

Patchy colloidal particles offer a unique platform to explore and investigate spatially inhomogeneous colloidal interactions. In the present work we provide direct, in situ experimental observation at the single particle level on the colloidal interaction driven formation of a heterodimer, consisting of a patchy nanorod and a sphere. The gold nanorods employed during the experiments feature positively charged tip regions, while the side of the rods is covered by surface grafted PEG. The driving force of the assembly is the electric double layer interaction between the nanorod and the nanosphere possessing opposite surface charge. The great advantage of using gold heterodimers is that their optical scattering spectrum characteristics are known to be very sensitive to the actual structure of the assembly due to plasmon hybridization. This was exploited to determine the structure of the heterodimer in situ upon formation in aqueous medium. The results indicate, that despite the attractive patches being located at the nanorod tips, for the given particle pairs the spheres readily bind to the side region of the nanorods in the aqueous medium during the assembly. Finite element simulations of the electric double layer interaction reveal that this is the energetically favorable configuration for the given heterodimer. This work demonstrates the potential of in situ experiments performed at single particle level for the characterization of self-assembling structures, which can contribute to the development of rationally designed nanoscale building blocks.

Role of temperature-dependent spin model parameters in ultra-fast magnetization dynamics.

In the spirit of multi-scale modelling magnetization dynamics at elevated temperature is often simulated in terms of a spin model where the model parameters are derived from first principles. While these parameters are mostly assumed temperature-independent and thermal properties arise from spin fluctuations only, other scenarios are also possible. Choosing bcc Fe as an example, we investigate the influence of different kinds of model assumptions on ultra-fast spin dynamics, where following a femtosecond laser pulse, a sample is demagnetized due to a sudden rise of the electron temperature. While different model assumptions do not affect the simulational results qualitatively, their details do depend on the nature of the modelling.

Assembling patchy nanorods with spheres: limitations imposed by colloidal interactions.

For gold nanorods the intrinsic shape-anisotropy offers the prospect of anisotropic assembly, provided that their region-selective surface modification can be realized. Here we developed nanorods with a patchy surface chemistry, featuring positively charged molecules in the tip region and polymer molecules at the sides by careful control of molecule concentrations during ligand exchange. When these patchy nanorods are assembled with small negatively charged spherical particles, electric double layer interaction can direct the assembly of two nanospheres at the opposite ends of the nanorods. The PEG chains promote the selectivity of the procedure. As the size of the nanospheres increases, they start to shift towards the side of the nanorod due to increased van der Waals interaction. When the relative size of the nanospheres is even larger, only a single nanosphere is assembled, but instead of the tip region, they are attached to the side of the nanorods. The apparent cross-over of the region-selectivity can be interpreted in terms of colloidal interactions, i.e. the second spherical particle is excluded due to nanosphere-nanosphere electric double layer repulsion, while the large vdW attraction results in a side positioning of the single adsorbed spherical particle. The results underline the importance of absolute values of the different interaction strengths and length scales in the programmed assembly of patchy nanoscale building blocks.

Magnetism of Gadolinium: A First-Principles Perspective.

By calculating the spectral density of states in the ferromagnetic ground state and in the high temperature paramagnetic phase we provide the first concise study of finite temperature effects on the electronic structure of the bulk and the surface of gadolinium metal. The variation of calculated spectral properties of the Fermi surface and the density of states in the bulk and at the surface are in good agreement with recent photoemission experiments performed in both ferromagnetic and paramagnetic phases. In the paramagnetic state we find vanishing spin splitting of the conduction band, but finite local spin moments both in bulk and at the surface. We clearly demonstrate that the formation of these local spin moments in the conduction band is due to the asymmetry of the density of states in the two spin channels, suggesting a complex, non-Stoner behavior. We, therefore, suggest that the vanishing or nearly vanishing spin splitting of spectral features cannot be used as an indicator for Stoner-like magnetism.

Evolution of magnetism on a curved nano-surface.

To design custom magnetic nanostructures, it is indispensable to acquire precise knowledge about the systems in the nanoscale range where the magnetism forms. In this paper we present the effect of a curved surface on the evolution of magnetism in ultrathin iron films. Nominally 70 Å thick iron films were deposited in 9 steps on 3 different types of templates: (a) a monolayer of silica spheres with 25 nm diameter, (b) a monolayer of silica spheres with 400 nm diameter and (c) for comparison a flat silicon substrate. In situ iron evaporation took place in an ultrahigh vacuum chamber using the molecular beam epitaxy technique. After the evaporation steps, time differential nuclear forward scattering spectra, grazing incidence small angle X-ray scattering images and X-ray reflectivity curves were recorded. In order to reconstruct and visualize the magnetic moment configuration in the iron cap formed on top of the silica spheres, micromagnetic simulations were performed for all iron thicknesses. We found a great influence of the template topography on the onset of magnetism and on the developed magnetic nanostructure. We observed an individual magnetic behaviour for the 400 nm spheres which was modelled by vortex formation and a collective magnetic structure for the 25 nm spheres where magnetic domains spread over several particles. Depth selective nuclear forward scattering measurements showed that the formation of magnetism begins at the top region of the 400 nm spheres in contrast to the 25 nm particles where the magnetism first appears in the region where the spheres are in contact with each other.

Magnetic correlations beyond the Heisenberg model in an Fe monolayer on Rh(0 0 1).

Motivated by a recent experimental observation of a complex magnetic structure (Takada et al 2013 J. Magn. Magn. Mater. 329 95) we present a theoretical study of the magnetic structure of an Fe monolayer deposited on Rh(0 0 1). We use a classical spin Hamiltonian with parameters obtained from ab initio calculations and go beyond the usual anisotropic Heisenberg model by including isotropic biquadratic interactions. Zero-temperature Landau-Lifshitz-Gilbert spin dynamics simulations lead to a complex collinear spin configuration that, however, contradicts experimental findings. We thus conclude that higher order multi-spin interactions are likely needed to account for the magnetic ordering of the system.

The structure and properties of graphene on gold nanoparticles.

Graphene covered metal nanoparticles constitute a novel type of hybrid material, which provides a unique platform to study plasmonic effects, surface-enhanced Raman scattering (SERS), and metal-graphene interactions at the nanoscale. Such a hybrid material is fabricated by transferring graphene grown by chemical vapor deposition onto closely spaced gold nanoparticles produced on a silica wafer. The morphology and physical properties of nanoparticle-supported graphene are investigated by atomic force microscopy, optical reflectance spectroscopy, scanning tunneling microscopy and spectroscopy (STM/STS), and confocal Raman spectroscopy. This study shows that the graphene Raman peaks are enhanced by a factor which depends on the excitation wavelength, in accordance with the surface plasmon resonance of the gold nanoparticles, and also on the graphene-nanoparticle distance which is tuned by annealing at moderate temperatures. The observed SERS activity is correlated with the nanoscale corrugation of graphene. STM and STS measurements show that the local density of electronic states in graphene is modulated by the underlying gold nanoparticles.

Controlling the nanoscale rippling of graphene with SiO2 nanoparticles.

The electronic properties of graphene can be significantly influenced by mechanical strain. One practical approach to induce strain in graphene is to transfer atomically thin membranes onto pre-patterned substrates with specific corrugations. The possibility of using nanoparticles to impart extrinsic rippling to graphene has not been fully explored yet. Here we study the structure and elastic properties of graphene grown by chemical vapour deposition and transferred onto a continuous layer of SiO2 nanoparticles with diameters of around 25 nm, prepared on a Si substrate by the Langmuir-Blodgett technique. We show that the corrugation of the transferred graphene, and thus the membrane strain, can be modified by annealing at moderate temperatures. The membrane parts bridging the nanoparticles are suspended and can be reversibly lifted by the attractive forces between an atomic force microscope tip and graphene. This allows the dynamic control of the local morphology of graphene nanomembranes.

Spin-correlations and magnetic structure in an Fe monolayer on 5d transition metal surfaces.

We present a detailed first principles study on the magnetic structure of an Fe monolayer on different surfaces of 5d transition metals. We use the spin-cluster expansion technique to obtain parameters of a spin model, and predict the possible magnetic ground state of the studied systems by employing the mean field approach and, in certain cases, by spin dynamics calculations. We point out that the number of shells considered for the isotropic exchange interactions plays a crucial role in the determination of the magnetic ground state. In the case of Ta substrate we demonstrate that the out-of-plane relaxation of the Fe monolayer causes a transition from ferromagnetic to antiferromagnetic ground state. We examine the relative magnitude of nearest neighbour Dzyaloshinskii-Moriya (D) and isotropic (J) exchange interactions in order to get insight into the nature of magnetic pattern formations. For the Fe/Os(0 0 0 1) system we calculate a very large D/J ratio, correspondingly, a spin spiral ground state. We find that, mainly through the leading isotropic exchange and Dzyaloshinskii-Moriya interactions, the inward layer relaxation substantially influences the magnetic ordering of the Fe monolayer. For the Fe/Re(0 0 0 1) system characterized by large antiferromagnetic interactions we also determine the chirality of the 120° Néel-type ground state.

Various nanostructures on macroscopically large areas prepared by tunable ion-swelling.

Various nanostructures were fabricated by ion irradiation on large area (100) Si surfaces covered by colloidal Langmuir-Blodgett films as nanolithographic masks. The ordered structure of the Langmuir-Blodgett monolayer composed from spherical Stöber silica particles of 200 nm and 450 nm diameter offer the possibility to form local surface swelling patterns during the ion bombardment step. Utilizing the dependence of the surface morphology on the irradiation parameters the tunability of nanostructuring was studied for 40 keV Ar+ and 500 keV Xe2+ ions. We show that the periodicity of the resulted surface pattern is determined by the size of the masking particles, while the height of nanostructures can be tuned by the ion fluence. The quality of projection of the nanomask contours to the substrate-the contrast of masking-can be set by choosing appropriate ion energy, thereby determining the curvature of the surface pattern. Moreover, deformation of the nanomask due to ion-nanoparticle interactions should be taken into account since these effects can be also utilized for tailoring various structures. The silica masking layers before and after ion irradiation and the resulting Si surface patterns were investigated by field emission scanning electron microscopy and atomic force microscopy analysis.

Dendrodendritic connections between the cochlear efferent neurons in guinea pig.

The outer hair cells of organ of Corti are innervated by the efferent neurons of medial olivocochlear neurons (MOC) of the brainstem which modify the cochlear auditory processing and sensitivity. Most of the MOC neurons are excited by a dominant ear and only a small portion of them is excited by both ears resulting in a binaural facilitation. The functional role of the feedback system between the organ of Corti and the cochlear efferent neurons is the protection of the ear from acoustic injury. The rapid impulse propagation in the bilateral olivocochlear system is suggestive of an electrotonic interaction between the bilateral olivocochlear neurons. The morphological background of the MOC pathway is not yet completely characterized. Therefore, we have labeled the bilateral cochlear nerves with different neuronal tracers in guinea pigs. In the anesthetized animals the cochlear nerves were exposed in the basal part of the modiolus and labeled simultaneously with different retrograde fluorescent tracers. By using confocal laser scanning microscope we could detect close appositions between the dendrites of the neurons of bilateral MOC. The distance between the neighboring profiles suggested close membrane appositions without interposing glial elements. These connections might serve as one of the underlying mechanisms of the binaural facilitation mediated by the olivocochlear system.

Examination of claudin-1 expression in patients undergoing liver transplantation owing to hepatitis C virus cirrhosis.

The cell adhesion molecule claudin-1 (CLDN-1) is a well known co-factor for the cell entry of hepatitis C virus (HCV). We examined 24 hepatic biopsies from liver transplant patients. Reverse transcriptase polymerase chain reaction (RT-PCR) and immunohistochemistry were performed according to standard procedures. RT-PCR results were shown as relative expression (ΔCT) with beta-actin as the reference gene. Immunohistochemistry results are shown by morphometry. The CLDN-1 mRNS expression rate was significantly lower when the patient displayed favorably with an unsatisfactory to antiviral therapy 0.756 ± 0.249 versus 1.304 ± 0.28 (P=.012). There was also a strong positive correlation between CLDN-1 protein expression and liver fibrosis (Pearson correlation coefficients: r=0.476; P=.034).

Cytokine profiles in women with different subtypes of major depressive disorder.

BACKGROUND: Depression has been associated with activation of the immune system. Some studies have shown increased levels of pro-inflammatory cytokines in patients with major depressive disorder (MDD), but conflicting results also have been described. METHODS: Forty-six unmedicated women with MDD were classified in subgroups (melancholic vs. non-melancholic; acute vs. chronic; severe vs. moderate, and episodic vs. recurrent presentations) and compared with 41 healthy controls. Evaluations of serum IL-1beta, IL-6, IFN-gamma and cortisol were performed on both groups. Patients were evaluated prior and after antidepressant treatment. RESULTS: The sub-classification of depression did not predict differences in cytokine levels. Patients currently depressed had similar levels of cytokines and cortisol as healthy controls. After remission of the symptoms, patients with MDD evolved with enhancement of cytokine levels, but no differences were observed in cortisol levels. LIMITATIONS: In patient treatment, two different classes of antidepressants were applied. The dexamethasone/CRH test was not performed to evaluate the HPA axis. CONCLUSIONS: Out-patient women diagnosed with MDD exhibited normal levels of both cortisol and cytokines before treatment, yet demonstrated an increase in cytokines after antidepressant treatment. In some patients with MDD, the presence of acute stress due to hospitalization may indeed contribute and justify the usual finding of higher levels in both cortisol and cytokines.

Brain-immune interactions and disease susceptibility.

Many studies have established the routes by which the immune and central nervous (CNS) systems communicate. This network of connections permits the CNS to regulate the immune system through both neuroendocrine and neuronal pathways. In turn, the immune system signals the CNS through neuronal and humoral routes, via immune mediators and cytokines. This regulatory system between the immune system and CNS plays an important role in susceptibility and resistance to autoimmune, inflammatory, infectious and allergic diseases. This review focuses on the regulation of the immune system via the neuroendocrine system, and underlines the link between neuroendocrine dysregulation and development of major depressive disorders, autoimmune diseases and osteoporosis.

Recovery of pigments from Origanum majorana L. by extraction with supercritical carbon dioxide.

Extraction of pigments (chlorophylls and carotenoids) from marjoram (Origanum majorana L.) with supercritical carbon dioxide was investigated. The aim of this study was to map the effects of extraction pressure and temperature on the yield of coloring materials by applying a 3(2) full factorial design with three repeated tests in the center of the design. For comparison, laboratory and pilot plant Soxhlet extractions were carried out using ethanol and n-hexane solvents. The compositions of pigments in marjoram extracts were determined by HPLC. Similar amounts of carotenoids, in addition to 40% of chlorophylls and their derivatives, were recovered from the supercritical fluid extraction, in comparison to the ethanol Soxhlet extraction.

Hydrogen-bonded hexagonal and pseudo-hexagonal grid motifs in supramolecular cobalt(II) and nickel(II) cupferronato complexes incorporating neutral N-donors with intermolecular NH2 connectors and solvent molecules.

The cobalt(II) and nickel(II) cupferronato (N-nitroso-N-phenylhydroxylaminato) mixed-ligand complexes of 2-aminopyridine (2-NH(2)py) [Co(PhN(2)O(2))(2)(2-NH(2)py)(2)] (1), [Ni(PhN(2)O(2))(2)(2-NH(2)py)(2)] (2) and 2,6-diamino-4-phenyl-1,3,5-triazine (dpt) [Co(PhN(2)O(2))(2)(dpt)(2)].[Co(PhN(2)O(2))(2)(EtOH)(2)] (3) have been synthesized and characterized by X-ray diffraction analysis. The cobalt (1) and nickel (2) complexes are isostructural. The crystal lattice of (3) contains different neutral cobalt(II) complexes [Co(PhN(2)O(2))(2)(dpt)(2)] (3a) and [Co(PhN(2)O(2))(2)(EtOH)(2)] (3b). Molecules of (1)-(3) contain octahedral metal centres with all-cis-(1) and -(2) and all-trans-(3) disposal of the ligands. Intramolecular N-H.O hydrogen bonding between the NH(2) groups and the O atom of the cupferronato anion can be observed in (1)-(3). Intermolecular N-H.O and N-H.N interactions between symmetry-related molecules of (1) and (2) led to hexameric aggregates which connect through common edges into a two-dimensional supramolecular network of hexagonal-grid type. In complex (3) the self-complementary dpt units of the (3a) molecules are maintained by intermolecular N-H.N hydrogen bonds, generating infinite chains. These (3a) chains are crosslinked by the (3b) subunits via N-H.O and O-H.N hydrogen bonds, thus completing the parallel two-dimensional supramolecular network consisting of pseudo-hexagonal-grid sheets. In each crystal structure the two-dimensional supramolecular networks are controlled by both hydrogen bonds and pi.pi stacking interactions.

Effect of late surgery for acquired esotropia on visual evoked potential.

PURPOSE: To asses the effect of strabismus surgery on visual evoked potential (VEP) amplitude after age 5 years in children with acquired esotropia. METHODS: Visual evoked potentials to binocular and monocular pattern reversal stimulation were recorded in 10 children aged 5 to 6 years before and 3 months after surgical correction of their esotropia. Visual function (fusion) was tested by synoptophore after strabismus surgery. Electrophysiological and clinical data were correlated following surgical intervention. RESULTS: A significant increase in pattern VEP amplitudes was noted following strabismus surgery. Visual evoked potential changes were most prominent on binocular stimulation. Binocular fusion showed similarly significant improvement after intervention. Postoperative VEP data, however, were not consistently correlated with functional improvement. CONCLUSION: Surgical intervention in esotropia, even if performed years beyond the end of the classical critical period, can have a strong effect on binocular VEPs and a beneficial effect on the development of binocular fusion.

Supercritical carbon dioxide extraction and fractionation of fennel oil.

Ground fennel seeds were extracted with supercritical carbon dioxide. Small-scale subsequent extractions of the same sample showed that the composition of volatile compounds was changed with the extension of extraction time and only principal volatile components (limonene, fenchone, methylchavicol, and anethole) were present in the last-extracted sample. Fennel oil was successfully fractionated into the essential oil rich and fatty oil rich products in pilot-scale apparatus using two separators in series. Designed experiments were carried out to map the effects of pressure and temperature in the first separator on the yields and compositions of the products. The minimum level of the total undesired components in both essential oil rich and fatty oil rich products appeared at a pressure of 80-84 bar and a temperature of 31-35 degrees C in the first separator. Supercritical CO(2) extraction of fennel seeds resulted in higher yield (10.0%) than steam distillation (3.0%), almost the same yield as hexane extraction (10.6%), and lower yield than alcohol extraction (15.4%). Analysis of the volatile compounds revealed the significant difference of the composition in distilled oil and oleoresins prepared by CO(2) and solvent extractions. Sensory evaluation showed that the CO(2) extraction product and distilled oil were more intense in odor and taste than alcohol and hexane extracts.