Paternal stress alters synaptic density and expression of GAP-43, GRIN1, M1 and SYP genes in the hippocampus and cortex of offspring of stress-induced male rats.

Adverse experiences during pregnancy have a negative impact on the neuronal structure and behavior of offspring, but the effects of a father's life events on the outcome of progeny are scarce. The present study is intended to investigate whether paternal stress affects the offspring brain structure, especially those regions concerned with learning and formation of memory, namely the hippocampus (HC) and prefrontal cortex (PFC), and also the expression of certain genes linked to learning and memory in the offspring. Induced stress to male rats by five stressors, one per day followed by allowing them to mate with the normal, unstressed female. Synaptophysin immunoreactivity was assessed in the tissue sections of the HC and PFC as well as expression of genes concerned with learning and memory was evaluated by RT-PCR in the progeny of stress-received males. The progeny of stressed rats had reduced antisynaptophysin immunoreactivity in the HC and PFC. The synaptic density in HC was less in the A-S (Offspring of male rats who received stress during adulthood) and PA-S (offspring of male rats who received stress during both adolescence and adulthood) than in P-S (offspring of male rats who received stress during adolescence) and C-C (offspring of control) groups. Similar results were observed even in the PFC. The results of post hoc tests proved that the HC and PFC of the progeny of stress-exposed rats exhibited considerably less synaptic density than control (P<0.05), and the levels of expression of GAP-43, GRIN1, M1, and SYP genes in HC and PFC were down-regulated. This study concludes that paternal adverse experiences can affect the offspring's synaptic plasticity and also the genes, which can regulate learning and formation of memory.

Os4+ Instability in the Pyrochlore Structure: Tl2-xBixOs2O7-y.

Osmium-containing oxides are rare due to the difficulty in stabilizing complex structures with a fixed stoichiometry and metastability of the phases. Bismuth-substituted thallium osmate pyrochlore samples, Tl2-xBixOs2O7-y, were synthesized using solid-state reactions where the solubility limit was found to be approximately x = 1.4. Members of this solid solution were characterized by their structural, electronic, magnetic, and thermal properties to understand the influence of Bi3+ substitution on the ground state. The Os-containing pyrochlores crystallize in the ideal cubic pyrochlore structure (Fd3m), and the lattice parameter a was found to slightly increase as a function of Bi content. A possible interplay between structure and cation valence states was explored using both neutron powder diffraction and X-ray absorption spectroscopy, suggesting that a combination of Os4+/Os5+ and Tl1+/Tl3+ mixed valency throughout the solid solution allows for the stabilization of the pyrochlore structure. The system is metallic for the entire solid solution and predominantly exhibits temperature-independent paramagnetism. Specific heat measurements show an enhanced Sommerfeld coefficient, a possible flat-band signature. This system gave insight into the bonding preferences of Os, indicating a dependence on high oxidation states and mixed valence for the stability of complex structures.

Influence of Alkaline-Earth-Metal Substitutions on the Bismuth Ruthenate Structure: Bi2-xA'xRu2O6O'1-y (A' = Mg, Ca, Sr).

Solid solutions with the formula of Bi2-xA'xRu2O7-y (A' = Mg, Ca, Sr; 0 ≤ x ≤ 0.2 for Mg, 0 ≤ x ≤ 1 for Ca, and 0 ≤ x ≤ 0.5 for Sr) have been synthesized and characterized. The crystal structures for these phases are found to be in the pyrochlore family, crystallizing in the cubic space group Fd3̅m with complex A/A' cation coordination environments. The Bi cation is found to be off-center from the ideal position because of a lone-pair distortion, while the positions of the substituted A' cations vary based on the size and ionicity. The neutron structure refinements reveal a similar propensity to off-center regarding Ca and Sr, while Mg features the largest static displacement of up to 0.48 Å. Interestingly, this is one of only two known pyrochlores with Mg2+ located in an 8-coordinated site. The average Ru oxidation state for each substitution is found to increase, and charge compensates for the lower divalent A' substitution. The solid solutions show temperature-independent resistance across the series with small changes in magnitude that scale with the amount of substitution, while displaying Pauli paramagnetic behavior throughout.

Sofosbuvir plus ribavirin in treatment-naïve patients with chronic hepatitis C virus genotype 1 or 3 infection in India.

Until 2014, pegylated interferon plus ribavirin was the recommended standard of care for the treatment of chronic hepatitis C virus (HCV) infection in India. This open-label phase 3b study, conducted across 14 sites in India between 31 March 2014 and 30 November 2015, evaluated the efficacy and safety of sofosbuvir plus ribavirin therapy among treatment-naïve patients with chronic genotype 1 or 3 HCV infection. A total of 117 patients with genotype 1 or 3 HCV infection were randomized 1:1 to receive sofosbuvir 400 mg and weight-based ribavirin (1000 or 1200 mg) daily for 16 or 24 weeks. Among those with genotype 1 infection, the primary efficacy endpoint of sustained virologic response at 12 weeks post-treatment (SVR12) was reported in 90% (95% confidence intervals [CI], 73-98) and 96% (95% CI, 82-100) of patients following 16 and 24 weeks of treatment, respectively. For patients with genotype 3 infection, SVR12 rates were 100% (95% CI, 88-100) and 93% (95% CI, 78-99) after 16 and 24 weeks of therapy, respectively. Adverse events, most of which were mild or moderate in severity, occurred in 69% and 57% of patients receiving 16 and 24 weeks of treatment, respectively. The most common treatment-emergent adverse events were asthenia, headache and cough. Only one patient in the 24-week group discontinued treatment with sofosbuvir during this study. Overall, sofosbuvir plus ribavirin therapy achieved SVR12 rates ≥90% and was well tolerated among treatment-naïve patients with chronic genotype 1 or 3 HCV infection in India.

Bi2-xCaxIr2O6+y Pyrochlore Phases: Structure and Properties with Varied Ir Oxidation State from 3.9+ to 4.3.

Pyrochlore phases Bi2-xCaxIr2O6Oy' with x from 0.0 to 1.0 have been evaluated based on Rietveld analysis of neutron diffraction data, electrical resistivity and thermopower data from 3 to 756 K, and magnetic susceptibility data from 3 to 298 K. The average Ir oxidation state is less than 4+ at low x, above 4+ for high x, and is very close to 4+ at x = 0.5. All samples show metallic properties with an electrical resistivity of ∼10-3 Ω·cm at room temperature. For low x, the sign of the Seebeck coefficient is negative at low temperature but becomes positive at high temperature. For high x, the sign of the Seebeck coefficient is positive from 3 to 756 K. Magnetic measurements indicate no magnetic ordering down to 3 K for all values of x. All Bi is in its ideal position for all values of x, but much of the Ca is strongly displaced from the ideal A cation site. This displacement of Ca apparently only occurs when there is an adjacent vacancy at the O' site.

Structure and Properties of Ir-Containing Oxides with Large Spin-Orbit Coupling: Ba2In(2-x)Ir(x)O(5+δ).

In this work, the solid solution series Ba2In(2-x)Ir(x)O5+δ (x = 0-1.4, 2) was synthesized, and its structural, magnetic, and charge-transport properties were measured. With increasing Ir content, three transitions in the room-temperature structure were observed: orthorhombic to tetragonal to cubic to a monoclinic distortion of a hexagonal BaTiO3 structure. Neutron diffraction shows Ba2In(1.6)Ir(0.4)O5.4 to be cubic and Ba2InIrO6 to be monoclinic, the latter contrary to previously published X-ray diffraction refinements. Magnetization measurements show Curie-Weiss behavior for x = 0.2-0.6, which arises from nearly 50:50 ratio of Ir(V) and Ir(VI). To our knowledge, this is the first time Ir(VI) has been stabilized with standard solid-state methods under ambient conditions. The electrical resistivity measurements show all the compounds studied are semiconducting and that resistivity decreases with increasing Ir content, suggesting the proximity to a metal-insulator transition. A sign reversal in the high-temperature Seebeck coefficient is observed indicating both electron and hole charge transport.

From Serendipity to Rational Design: Tuning the Blue Trigonal Bipyramidal Mn3+ Chromophore to Violet and Purple through Application of Chemical Pressure.

We recently reported that an allowed d-d transition of trigonal bipyramidal (TBP) Mn3+ is responsible for the bright blue color in the YIn1-xMnxO3 solid solution. The crystal field splitting between a'(dz2) and e'(dx2-y2, dxy) energy levels is very sensitive to the apical Mn-O distance. We therefore applied chemical pressure to compress the apical Mn-O distance in YIn1-xMnxO3, move the allowed d-d transition to higher energy, and thereby tune the color from blue to violet/purple. This was accomplished by substituting smaller cations such as Ti4+/Zn2+ and Al3+ onto the TBP In/Mn site, which yielded novel violet/purple phases. The general formula is YIn1-x-2y-zMnxTiyZnyAlzO3 (x = 0.005-0.2, y = 0.1-0.4, and z ≤ 0.1), where the color darkens with the increasing amount of Mn. Higher y or small additions of Al provide a more reddish hue to the resulting purple colors. Substituting other rare earth cations for Y has little impact on color. Crystal structure analysis by neutron powder diffraction confirms a shorter apical Mn-O distance compared with that in the blue YIn1-xMnxO3. Magnetic susceptibility measurements verify the 3+ oxidation state for Mn. Diffuse reflection spectra were obtained over the wavelength region 200-2500 nm. All samples show excellent near-infrared reflectance comparable to that of commercial TiO2, making them ideal for cool pigment applications such as energy efficient roofs of buildings and cars where reducing solar heat to save energy is desired. In a comparison with commercial purple pigments, such as Co3(PO4)2, our pigments are much more thermally stable and chemically inert, and are neither toxic nor carcinogenic.

Influence of Structural Disorder on Hollandites A(x)Ru4O8 (A(+) = K, Rb, Rb(1-x)Na(x)).

Structural disorder can play an important role in the electrical properties of correlated materials. In this work we examine the average and local disorder in hollandites A(x)Ru4O8 (A(+) = K, Rb, Rb(1-x)Na(x)) through neutron total scattering techniques. Samples with A(+) = Rb, Rb(1-x)Na(x) exhibit the largest amount of local disorder as evidenced by higher atomic displacement parameters, and as a result, a weakened temperature dependence of the resistivity is observed upon cooling as compared to K(x)Ru4O8. All samples exhibit anisotropic resistivity that is dominated by metallic conductivity at lower temperatures, and this is corroborated by Pauli paramagnetic behavior throughout the measured temperature regime.

trans-4,4'-Dihydroxystilbene (DHS) protects PC12 cells from oxidative damage but induces reactive oxygen species-mediated apoptosis in SHSY-5Y cell line.

Polyphenols can exert both, antioxidant and pro-oxidant properties, depending on cell types as well as their concentrations. Hence, it was of interest to examine if the naturally occurring resveratrol analog, trans-4,4'-dihydroxystilbene (DHS) also exert both these activities in a biphasic or cell-specific manner. In this study, we established the cytoprotective action of DHS against hydrogen peroxide (H2O2)-induced apoptotic death of the PC12 cells. DHS reduced mitochondrial membrane permeabilization and deactivated reactive oxygen species (ROS)-mediated caspase-3 activation in the H2O2-treated PC12 cells. However, it induced apoptosis in the human neuroblastoma SHSY-5Y cell line by destabilizing mitochondrial membrane, augmenting ROS and activating caspapse-3. DHS showed better activity than resveratrol in both the chosen models.

Magnetic properties and electronic structure of manganese-based blue pigments: a high-frequency and -field EPR study.

A variety of new oxide-based materials based on hexagonal phase of YInO3 have been recently described. In some of these materials, the In(III) ions are substituted by Mn(III), which finds itself in a trigonal-bipyramidal (TBP) coordination environment. While YInO3 is colorless and YMnO3 is black, mixed systems YIn1-xMnxO3 (0.02 < x < 0.25) display intense blue color and have been proposed as novel blue pigments. Since the Mn(III) ion is paramagnetic, its presence imparts distinct magnetic properties to the whole class of materials. These properties were investigated by electron paramagnetic resonance (EPR) in its high-frequency and -field version (HFEPR), a technique ideally suited for transition metal ions such as Mn(III) that, in contrast to, for example, Mn(II), are difficult to study by EPR at (conventional) low frequency and field. YIn1-xMnxO3 with 0.02 < x < 0.2 exhibited high-quality HFEPR spectra up to room temperature that could be interpreted as arising from isolated S = 2 paramagnets. A simple ligand-field model, based on the structure and optical spectra, explains the spin Hamiltonian parameters provided by HFEPR, which were D = +3.0 cm(-1), E = 0; g⊥ = 1.99, g∥ = 2.0. This study demonstrates the general applicability of a combined spectroscopic and classical theoretical approach to understanding the electronic structure of novel materials containing paramagnetic dopants. Moreover, HFEPR complements optical and other experimental methods as being a sensitive probe of dopant level.

True composition and structure of hexagonal "YAlO3", actually Y3Al3O8CO3.

The discovery of a brilliant-blue color upon the introduction of Mn(3+) to the trigonal-bipyramidal (TBP) sites in YInO(3) has led to a search for other hosts for Mn(3+) in TBP coordination. An obvious choice would be YAlO(3). This compound, which has only been prepared through a citrate precursor route, has long been considered isostructural with YInO(3). However, Mn(3+) substitutions into YAlO(3) have failed to produce a product with the anticipated color. We find that the hexagonal structure for YAlO(3) with Al in TBP coordination proposed in 1963 cannot be correct based on its unit cell dimensions and bond-valence sums. Our studies indicate instead that all, or nearly all, of the Al in this compound has a coordination number (CN) of 6. Upon heating in air, this compound transforms to YAlO(3), with the perovskite structure liberating CO(2). The compound long assumed to be a hexagonal form of YAlO(3) is actually an oxycarbonate with the ideal composition Y(3)Al(3)O(8)CO(3). The structure of this compound has been characterized by powder neutron and X-ray diffraction data obtained as a function of temperature, magic-angle-spinning (27)Al NMR, Fourier transform infrared, and transmission electron microscopy. Refinement of neutron diffraction data indicates a composition of Y(3)Al(3)O(8)CO(3). We find that the hexagonal structures of YGaO(3) and YFeO(3) from the citrate route are also stabilized by small amounts of carbonate. Surprisingly, Y(3)Al(3)O(8)CO(3) forms a complete solid solution with YBO(3) having tetrahedral borate groups. Other unlikely solid solutions were prepared in the YAlO(3)-YMnO(3), YAlO(3)-YFeO(3), YAlO(3)-YBO(3), YBO(3)-YMnO(3), YBO(3)-YFeO(3), and YBO(3)-YGaO(3) systems.

Parametric investigation of W-EDM factors for machining AM60B conductive biomaterial.

Wire-electrical discharge machining (W-EDM) is a precise and efficient non-traditional technology employed to cut intricate shapes in conductive biomaterials. These biomaterials are challenging to machine using traditional methods. This present study delves into the impact of various process parameters, namely discharge duration (Ddur), spark gap time (Stime), discharge voltage (Dvolt), and wire advance rate rate (Wadv). This research evaluates the impact of several factors on response variables, namely the machining rate (MR) and surface irregularity (SR), during the machining process of the AM60B magnesium alloy. The confirmation of the material used in the machining process is achieved via the utilisation of a scanning electron microscopy (SEM) image in conjunction with an energy dispersive spectroscopic (EDS) image. The experiment is designed as L9 orthogonal array by using Taguchi's approach, taking into account 4 factors with 3 levels. The objective of this experiment is to ascertain the most favourable values for machining parameters while working with AM60B magnesium alloy using brass wire. Through analysis of variance (ANOVA), the study confirms that wire advance rate (43.10%) is the most influencing parameter for machining rate and surface irregularity followed by spark gap time (33.91%) and discharge duration (11.48%). Additionally, The TOPSIS-CRITIC and the desirability approach were used in order to determine the optimum parameter combinations that provide the most favourable combined output. Confirmatory testing is used to evaluate the efficiency of the stated ideal conditions. The maximum improvement in Desirability approach is obtained at 4.56% and 4.193% for MR and SR respectively. The maximum improvement in TOPSIS approach is obtained at 1.77% and 2.78% for MR and SR respectively.

Divergent synthesis of 4-epi-fagomine, 3,4-dihydroxypipecolic acid, and a dihydroxyindolizidine and their ß-galactosidase inhibitory and immunomodulatory activities.

A divergent asymmetric synthesis of the titled iminosugars has been formulated starting from a chiral homoallyl alcohol as the versatile intermediate. The homoallyl alcohol was prepared by a highly diastereoselective Barbier reaction on a d-glucose-derived aldehyde. The protection of its hydroxyl function followed by reductive ozonolysis of the olefin and a subsequent one-pot three-step protocol involving a Staudinger reaction, reductive amination, and benzyloxy carbonyl protection yielded an important bicyclic furanopiperidine derivative. This was converted to the target compounds by following standard reactions. Among the synthesized compounds, 4-epi-fagomine (2b) was the best ß-galactosidase inhibitor, and it also prevented LPS-mediated activation of Raw 264.7 macrophage cells. Its congener, 3,4-dihydroxypipecolic acid (4b) also showed similar trends in its cytokine- and enzyme-inhibitory properties at a low concentration (10 µM) but was proinflammatory at higher concentrations. The bicyclic compound dihydroxyindolizidine (21) reduced the proinflammatory cytokine (IL-1ß and TNF-α) levels in the LPS-activated Raw 264.7 cells without showing any enzyme-inhibition activity.

Intense turquoise and green colors in brownmillerite-type oxides based on Mn5+ in Ba2In(2-x)Mn(x)O(5+x).

Brownmillerite-type oxides Ba(2)In(2-x)Mn(x)O(5+x) (x = 0.1-0.7) have been prepared and characterized. Magnetic measurements indicate that manganese in as-prepared samples is substituting predominantly as Mn(5+) for all values of x with observed paramagnetic spin-only moments close to values expected for two unpaired electrons. Electron paramagnetic resonance measurements indicate that this Mn(5+) is present in a highly distorted tetrahedral environment. Neutron diffraction structure refinements show that Mn(5+) occupies tetrahedral sites for orthorhombic (x = 0.1) and tetragonal (x = 0.2) phases. For Mn ≥ 0.3 samples, neutron refinements show that the phases are cubic with disordered cations and oxygen vacancies. The colors of the phases change from light yellow (x = 0) to intense turquoise (x = 0.1) to green (x = 0.2, 0.3) or to dark green (x ≥ 0.4). Under reducing conditions, Mn(5+) is reduced to Mn(3+), and Ba(2)In(2-x)Mn(x)O(5+x) phases become black Ba(2)In(2-x)Mn(x)O(5) phases still with the brownmillerite structure.

Structural investigation of the substituted pyrochlore AgSbO3 through total scattering techniques.

Polycrystalline samples of the pyrochlore series Ag(1-x)M(n)(x)SbO(3+x[(n-1)/2]) (M = Na, K, and Tl) have been structurally analyzed through total scattering techniques. The upper limits of x obtained were 0.05 for Na, 0.16 for K, and 0.17 for Tl. The Ag(+) cation occupies a site with inversion symmetry on a 3-fold axis. When the smaller Na(+) cation substitutes for Ag(+), it is displaced by about 0.6 Å perpendicular to the 3-fold axis to achieve some shorter Na-O bond distances. When the larger Tl(+) cation substitutes for Ag(+), it is displaced by about 1.14 Å along the 3-fold axis and achieves an environment typical of a lone pair cation. Some of the Tl(3+) from the precursor remains unreduced, leading to a formula of Ag(0.772(1))Tl(+)(0.13(2))Tl(3+)(0.036(1))SbO(3.036(1)). The position of the K(+) dopant was effectively modeled assuming that K(+) occupied the same site as Ag(+). The expansion of the lattice caused by substitution of the larger K(+) and Tl(+) cations results in longer Ag-O bond lengths, which would reduce the overlap of the Ag 4d and O 2p orbitals that compose the valence band maximum. Substitution of the smaller Na(+) results in a decrease in the Ag-O bond distance, thus increasing the overlap of the Ag 4d and O 2p orbitals. This will have a direct influence on the band composition and observed properties of this material of interest.

Effect of silicon carbide on kerf convergence and irregularity of the surface during abrasive water jet machining of fiber-metal hybrid composites.

The traditional way to machine hybrid composites is hard because they tend to break, have a high retraction, have a high service temperature, and have an uneven surface irregularity. For high-strength fiber/metal composite constructions, alternative machining methods have drawn interest as a solution to these problems. Current research focuses on enhancing the Abrasive Water Jet Machining process by optimizing its variables using a composite material of epoxy reinforced with silicon carbide, stainless steel wire mesh, and Kevlar. The variables assessed are the Nozzle-to-substrate gap (S), the Abrasive discharge molding and different percentages of silicon carbide (SiC) filler (0%, 3%, and 6% by weight), three different types of hybrid laminates (H1, H2, and H3) were produced. The response surface method (RSM) was utilized in this learning, specifically on a central composite design, to calculate and optimize machining variables based on the Kerf convergence ratio (Kt) and Surface irregularity (Ra) as responses. According to the results, the traverse feed velocity, Abrasive discharge proportion, and Nozzle-to-substrate gap are the critical factors in determining Surface irregularity and Kerf convergence width (H1 laminate) for a fiber/metal laminate with 0%, 3% and 6% weight fraction. In the case of a 3% weight fraction H2 laminate, the traverse feed velocity was identified as the primary factor affecting the Kerf convergence ratio. In contrast, traverse feed velocity and Nozzle-to-substrate gap had the most significant influence on Surface irregularity. The findings also indicated that S, followed by Abrasive discharge proportion and traverse feed velocity, are the variables that have the most significant influence when cutting 6 wt% SiC filler particle fiber/metal laminate (H3 laminate). For Surface irregularity, the combination of traverse feed velocity and Nozzle-to-substrate gap had the most significant impact. To validate the optimization results, confirmatory tests was conducted, and the findings were very similar to the experimental values, indicating the accuracy and effectiveness of the optimization process. To better understand the manufacturing processes, a scanning electron microscope was used to examine the morphological features of the machined surfaces, such as delamination, fibre breakage, and fibre pull-out.

New layered compounds with honeycomb ordering: Li3Ni2BiO6, Li3NiM'BiO6 (M' = Mg, Cu, Zn), and the delafossite Ag3Ni2BiO6.

The new layered compound Li(3)Ni(2)BiO(6) has been prepared by a solid-state reaction. It crystallizes in the monoclinic C2/m space group; its lamellar structure is characterized by a honeycomb ordering between Ni(2+) and Bi(5+) within the slabs, while Li(+) ions occupy octahedral sites in the interslab space. Stacking defects weakly alter the XRD pattern. By substitution of half of the nickel ions, the new phases Li(3)NiM'BiO(6) (M' = Mg, Cu, Zn) isostructural with Li(3)Ni(2)BiO(6) have been synthesized under similar conditions. All these compounds demonstrate paramagnetic behavior at high temperature, and Li(3)Ni(2)BiO(6) exhibits an antiferromagnetic ordering at 5.5 K. By topotactic molten salt ionic exchange, the new delafossite compound Ag(3)Ni(2)BiO(6) has been also obtained and characterized.

New oxides showing an intense blue color based on Mn3+ in trigonal-bipyramidal coordination.

Substitution of Mn(3+) into the trigonal-bipyramidal sites of oxides with YbFe(2)O(4)-related structures produces an intense blue color because of an allowed d-d transition. This has been demonstrated utilizing a variety of hosts including ScAlMgO(4), ScGaMgO(4), LuGaMgO(4), ScGaZnO(4), LuGaZnO(4), and LuGaO(3)(ZnO)(2). The hue of the blue color can be controlled by the choice of the host.

New oxides showing an intense orange color based on Fe3+ in trigonal-bipyramidal coordination.

Hexagonal YIn(1-x)Fe(x)O(3) phases have been prepared and characterized. The coordination for the In/Fe site in this structure is trigonal-bipyramidal. The colors of the phases change from yellow to orange to dark red with increasing Fe content. Magnetic measurements confirm high-spin Fe(3+) for all phases.

Undulating layers in a new rhodate network: structure of Bi(1.4)CuORh5O10.

A new rhodate, Bi(1.4)CuRh(5)O(11), with an hitherto unknown channel structure containing undulating layers of RhO(6) octahedra sharing corners and edges has been discovered and its structure refined from single crystal X-ray diffraction data. The channels contain Bi(3+), Cu(2+), and some O strongly bound to Cu. The Cu coordination is distorted square planar. Mixed Rh(3+)/Rh(4+) valency leads to significant electrical conductivity.