CCR2-dependent CX3CR1+ colonic macrophages promote Enterococcus faecalis dissemination.

Enterococci are common commensal bacteria that colonize the gastrointestinal tracts of most mammals, including humans. Importantly, these bacteria are one of the leading causes of nosocomial infections. This study examined the role of colonic macrophages in facilitating Enterococcus faecalis infections in mice. We determined that depletion of colonic phagocytes resulted in the reduction of E. faecalis dissemination to the gut-draining mesenteric lymph nodes. Furthermore, we established that trafficking of monocyte-derived CX3CR1-expressing macrophages contributed to E. faecalis dissemination in a manner that was not reliant on CCR7, the conventional receptor involved in lymphatic migration. Finally, we showed that E. faecalis mutants with impaired intracellular survival exhibited reduced dissemination, suggesting that E. faecalis can exploit host immune cell migration to disseminate systemically and cause disease. Our findings indicate that modulation of macrophage trafficking in the context of antibiotic therapy could serve as a novel approach for preventing or treating opportunistic infections by disseminating enteric pathobionts like E. faecalis.

Competition between Anion-Deficient Oxide and Oxyhydride Phases during the Topochemical Reduction of LaSrCoRuO6.

Binary metal hydrides can act as low-temperature reducing agents for complex oxides in the solid state, facilitating the synthesis of anion-deficient oxide or oxyhydride phases. The reaction of LaSrCoRuO6, with CaH2 in a sealed tube yields the face-centered cubic phase LaSrCoRuO3.2H1.9. The reaction with LiH under similar conditions converts LaSrCoRuO6 to a mixture of tetragonal LaSrCoRuO4.8H1.2 and cubic LaSrCoRuO3.3H2.13. The formation of the LaSrCoRuOxHy oxyhydride phases proceeds directly from the parent oxide, with no evidence for anion-deficient LaSrCoRuO6-x intermediates, in contrast with many other topochemically synthesized transition-metal oxyhydrides. However, the reaction between LaSrCoRuO6 and LiH under flowing argon yields a mixture of LaSrCoRuO5 and the infinite layer phase LaSrCoRuO4. The change to all-oxide products when reactions are performed under flowing argon is attributed to the lower hydrogen partial pressure under these conditions. The implications for the reaction mechanism of these topochemical transformations is discussed along with the role of the hydrogen partial pressure in oxyhydride synthesis. Magnetization measurements indicate the LaSrCoRuOxHy phases exhibit local moments on Co and Ru centers, which are coupled antiferromagnetically. In contrast, LaSrCoRuO4 exhibits ferromagnetic behavior with a Curie temperature above 350 K, which can be rationalized on the basis of superexchange coupling between the Co1+ and Ru2+ centers.

Influence of Cation Substitution on Cycling Stability and Fe-Cation Migration in Li3Fe3-xMxTe2O12 (M = Al, In) Cathode Materials.

Li3Fe3Te2O12 adopts a crystal structure, described in space group Pnnm, related to that of LiSbO3, in which Te6+, Fe3+, and Li+ cations reside in a partially ordered configuration within an hcp array of oxide ions. Chemical or electrochemical insertion of lithium is accompanied by a fully reversible migration of some of the Fe cations with an initial capacity of 120 mA h g-1 (2.85 Li per formula unit). Long-term cycling stability is limited by the facile reduction of Te6+ to elemental Te, which leads to cathode decomposition. Partial substitution of Fe by In suppresses Te6+ reduction, such that Li3Fe2InTe2O12 shows no sign of this cathode decomposition pathway, even after 100 cycles. In contrast, Al-for-Fe substitution is chemically limited to Li3Fe2.6Al0.4Te2O12 and appears to have almost no influence on cathode longevity. These features of the Li3Fe3-xMxTe2O12 system are discussed on the basis of a detailed structural analysis performed using neutron and synchrotron X-ray diffraction.

Disproportionation of Co2+ in the Topochemically Reduced Oxide LaSrCoRuO5.

Complex transition-metal oxides exhibit a wide variety of chemical and physical properties which are a strong function the local electronic states of the transition-metal centres, as determined by a combination of metal oxidation state and local coordination environment. Topochemical reduction of the double perovskite oxide, LaSrCoRuO6 , using Zr, yields LaSrCoRuO5 . This reduced phase contains an ordered array of apex-linked square-based pyramidal Ru3+ O5 , square-planar Co1+ O4 and octahedral Co3+ O6 units, consistent with the coordination-geometry driven disproportionation of Co2+ . Coordination-geometry driven disproportionation of d7 transition-metal cations (e.g. Rh2+ , Pd3+ , Pt3+ ) is common in complex oxides containing 4d and 5d metals. However, the weak ligand field experienced by a 3d transition-metal such as cobalt leads to the expectation that d7+ Co2+ should be stable to disproportionation in oxide environments, so the presence of Co1+ O4 and Co3+ O6 units in LaSrCoRuO5 is surprising. Low-temperature measurements indicate LaSrCoRuO5 adopts a ferromagnetically ordered state below 120 K due to couplings between S=1 /2 Ru3+ and S=1 Co1+ .

Ca2MnO3X (X = Cl, Br) Oxyhalides with 1-Dimensional Ferromagnetic Chains of Square-Planar S = 2 Mn3.

Mixed anion oxyhalides with the formula Ca2MnO3X (X = Cl, Br) are synthesized using solid-state reaction methods. These two materials crystallize in a novel structure type due to the small ionic radius of Ca and the strong Jahn-Teller effect of Mn3+. The resulting structure (space group Cmcm) contains one-dimensional chains of MnO4 square planes, with an angle of ∼120° between neighboring planes. At low temperatures, the two materials adopt magnetic arrangements, with ferromagnetic chains coupled antiferromagnetically. On applying a magnetic field, both materials experience spin-flop transitions.

Complex Magnetic Order in Topochemically Reduced Rh(I)/Rh(III) LaM0.5Rh0.5O2.25 (M = Co, Ni) Phases.

Topochemical reduction of the cation-disordered perovskite oxides LaCo0.5Rh0.5O3 and LaNi0.5Rh0.5O3 with Zr yields the partially anion-vacancy ordered phases LaCo0.5Rh0.5O2.25 and LaNi0.5Rh0.5O2.25, respectively. Neutron diffraction and Hard X-ray photoelectron spectroscopy (HAXPES) measurements reveal that the anion-deficient phases contain Co1+/Ni1+ and a 1:1 mixture of Rh1+ and Rh3+ cations within a disordered array of apex-linked MO4 square-planar and MO5 square-based pyramidal coordination sites. Neutron diffraction data indicate that LaCo0.5Rh0.5O2.25 adopts a complex antiferromagnetic ground state, which is the sum of a C-type ordering (mM5+) of the xy-components of the Co spins and a G-type ordering (mΓ1+) of the z-components of the Co spins. On warming above 75 K, the magnitude of the mΓ1+ component declines, attaining a zero value by 125 K, with the magnitude of the mM5+ component remaining unchanged up to 175 K. This magnetic behavior is rationalized on the basis of the differing d-orbital fillings of the Co1+ cations in MO4 square-planar and MO5 square-based pyramidal coordination sites. LaNi0.5Rh0.5O2.25 shows no sign of long-range magnetic order at 2 K - behavior that can also be explained on the basis of the d-orbital occupation of the Ni1+ centers.

Hole and Electron Doping of Topochemically Reduced Ni(I)/Ru(II) Insulating Ferromagnetic Oxides.

LaxSr2-xNiRuO6, LaxSr4-xNiRuO8, and LaxSr3-xNiRuO7 are, respectively, the n = ∞, 1, and 2 members of the (Lax/2Sr1-(x/2))nSr(Ni0.5Ru0.5)nO3n+1 compositional series. Reaction with CaH2, in the case of the LaxSr2-xNiRuO6 perovskite phases, or Zr oxygen getters in the case of the LaxSr4-xNiRuO8 and LaxSr3-xNiRuO7 Ruddlesden-Popper phases, yields the corresponding topochemically reduced (Lax/2Sr1-(x/2))nSr(Ni0.5Ru0.5)nO3n-1 compounds (LaxSr2-xNiRuO4, LaxSr4-xNiRuO6, and LaxSr3-xNiRuO5), which contain Ni and Ru cations in square-planar coordination sites. The x = 1 members of each series (LaSrNiRuO4, LaSr3NiRuO6, and LaSr2NiRuO5) exhibit insulating ferromagnetic behavior at low temperature, attributable to exchange couplings between the Ni1+ and Ru2+ centers they contain. Increasing the La3+ concentration (x > 1) leads to a reduction of some of the Ru2+ centers to Ru1+ centers and a suppression of the ferromagnetic state (lower Tc, reduced saturated ferromagnet moment). In contrast, increasing the Sr2+ concentration (x < 1) oxidizes some of the Ru2+ centers to Ru3+ centers and enhances the ferromagnetic coupling (increased Tc, increased saturated ferromagnet moment) for the n = ∞ and n = 2 samples but appears to have no influence on the magnetic ordering temperature of the n = 1 samples. The magnetic couplings and influence of doping are discussed on the basis of superexchange and direct exchange couplings between the square-planar Ni and Ru centers.

LaSrCo0.5Rh0.5O3.25 and LaSrNi0.5Rh0.5O3.25:Topochemically Reduced, Mixed Valence Rh(I)/Rh(III) Oxides.

Topochemical reduction of the n = 1 Ruddlesden-Popper phases LaSrCo0.5Rh0.5O4 and LaSrNi0.5Rh0.5O4 with Zr yields LaSrCo0.5Rh0.5O3.25 and LaSrNi0.5Rh0.5O3.25, respectively. Magnetization and XPS data reveal that while the rhodium centers in LaSrCo0.5Rh0.5O3.25 and LaSrNi0.5Rh0.5O3.25 have an average oxidation state of Rh2+, these are actually mixed valence Rh(I,III) compounds, with the disproportionation of Rh2+ driven by the favorability of locating d8 Rh1+ and d6 Rh3+ cations within square-planar and square-based pyramidal coordination sites, respectively.

Evidence of Paracrystalline Cation Order in the Ruddlesden-Popper Phase LaSr3NiRuO8 through Neutron Total Scattering Techniques.

Cation ordering in perovskite-derived phases can lead to a wealth of tunable physical properties. Ordering is typically driven by a large difference between the cation size and charge, but many Ruddlesden-Popper phases An+1BnO3n+1 appear to lack such B-site ordering, even when these differences are present. One such example is the "double" Ruddlesden-Popper n = 1 composition LaSr3NiRuO8. In this material, a lack of B-site ordering is observed through traditional crystallographic techniques, but antiferromagnetic ordering in the magnetism data suggests that B-site cation ordering is indeed present. Neutron total scattering, particularly analysis of the neutron pair distribution function, reveals that the structure is locally B-site-ordered below 6 Å but becomes slightly disordered in the midrange structure around 12 Å. This provides evidence for paracrystalline order in this material: cation ordering within a single perovskite sheet that lacks perfect registry within the three-dimensional stack of sheets. This work highlights the importance of employing a structural technique that can probe both the local and midrange order in addition to the crystallographic structure and provides a structural origin to the observed magnetic properties of LaSr3NiRuO8. Further, it is proposed that paracrystalline order is likely to be common among these layered-type oxides.

Hole and Electron Doping of the 4d Transition-Metal Oxyhydride LaSr3 NiRuO4 H4.

Hole or electron doping of phases prepared by topochemical reactions (e.g. anion deintercalation or anion-exchange) is extremely challenging as these low-temperature conversion reactions are typically very sensitive to the electron counts of precursor phases. Herein we report the successful hole and electron doping of the transition-metal oxyhydride LaSr3 NiRuO4 H4 by first preparing precursors in the range Lax Sr4-x NiRuO8 0.5

A Structurally Characterized Cobalt(I) σ-Alkane Complex.

A cobalt σ-alkane complex, [Co(Cy2 P(CH2 )4 PCy2 )(norbornane)][BArF 4 ], was synthesized by a single-crystal to single-crystal solid/gas hydrogenation from a norbornadiene precursor, and its structure was determined by X-ray crystallography. Magnetic data show this complex to be a triplet. Periodic DFT and electronic structure analyses revealed weak C-H→Co σ-interactions, augmented by dispersive stabilization between the alkane ligand and the anion microenvironment. The calculations are most consistent with a η1 :η1 -alkane binding mode.

Synthesis and Magnetism of Extended Solids Containing Transition-Metal Cations in Square-Planar, MO4 Coordination Sites.

With the exception of systems containing Cu2+, complex metal oxides containing paramagnetic transition-metal cations in square-planar coordination are rare. However, by either introducing chalcogenide, pnictide, or halide anions to form mixed-anion systems or by utilizing low-temperature topochemical reduction via anion deintercalation, an extensive range of phases containing square-planar MO4 units can be prepared. The crystal chemistry of a series of transition-metal A2MO2X2 oxyhalide and A2MO2B2X2 oxychalcogenide and oxypnictide phases is reviewed along with how their magnetic behavior changes as a function of the transition-metal and electron count. As a contrast, these mixed-anion phases are then compared to a series of topochemically reduced, metastable transition-metal oxides that also contain square-planar-coordinated transition metals, to more fully illustrate the magnetic properties of extended frameworks of square-planar MO4 units.

Structure and Magnetism of (La/Sr)2M0.5IrV0.5O4 and Topochemically Reduced (La/Sr)2M0.5IrII0.5O3 (M = Fe, Co) Complex Oxides.

Neutron powder diffraction data show that Sr2Fe0.5Ir0.5O4, Sr2Co0.5Ir0.5O4, and La0.5Sr1.5Co0.5Ir0.5O4 all adopt undistorted, n = 1 Ruddlesden-Popper structures in which the Ir5+ and Fe3+/Co3+/Co2+ cations are statistically disordered over all the octahedral coordination sites. Magnetization data indicate the two cobalt phases are spin glasses at low temperature, while Sr2Fe0.5Ir0.5O4 appears to adopt an antiferromagnetic state with very small magnetically ordered domains. Topochemical reduction with a Zr getter converts the tetragonal A2M0.5Ir0.5O4 phases to the corresponding orthorhombic A2M0.5Ir0.5O3 phases in which the Ir2+ and Fe2+/Co2+/Co1+ cations are located in approximately square-planar coordination sites. Magnetization data indicate Sr2Fe0.5Ir0.5O3 is a spin glass below TG ∼ 30 K, while Sr2Co0.5Ir0.5O3 appears to be antiferromagnetic below TN ∼ 25 K and La0.5Sr1.5Co0.5Ir0.5O3 shows no sign of magnetic order for T > 5 K. The magnetic behavior of both the A2M0.5Ir0.5O4 and A2M0.5Ir0.5O3 phases is discussed on the basis of metal d-electron count and structural features.

CaMn0.5Ir0.5O2.5: An Anion-Deficient Perovskite Oxide Containing Ir3.

Reaction between CaMn0.5Ir0.5O3 and NaH, either through solid-solid contact or via a gas mediated reaction process, yields the topochemically reduced phase CaMn0.5Ir0.5O2.5 in which Mn3+ and Ir3+ cations are located within a partially anion-vacancy disordered lattice. Magnetization data from CaMn0.5Ir0.5O2.5 can be fit by the Curie-Weiss law to yield C = 1.586 cm3 K mol-1 and θ = -86.9 K, consistent with a combination of S = 2, Mn3+ and S = 0, Ir3+. On cooling below T ∼ 110 K, the system undergoes a transition to a spin-glass state, consistent with the observed Mn/Ir cation disorder and frustration between Mn-O-Mn and Mn-O-Ir-O-Mn magnetic couplings. The degree of reduction and the observed anion-vacancy disorder are discussed on the basis of the d-orbital filling of the transition-metal cations.

Pressure-Induced Transitions in the 1-Dimensional Vanadium Oxyhydrides Sr2VO3H and Sr3V2O5H2, and Comparison to 2-Dimensional SrVO2H.

High-pressure X-ray diffraction measurements on the layered oxyhydrides Sr2VO3H and Sr3V2O5H2 reveal that both compounds undergo a pressure-induced rock-salt to CsCl (B1-B2) structural transition, similar to those observed in binary compounds (oxides, halides, chalcogenides, etc.). This structural transition, observed at 43 and 45 GPa in Sr2VO3H and Sr3V2O5H2, respectively, relieves almost all of the accumulated strain on the infinite V-O-V ladders, such that the V-O bond lengths are almost identical at 0 and 50 GPa but are substantially compressed at intermediate pressures. The resistances of both materials with 1-dimensional VO ladders decrease with increasing pressure, but unlike SrVO2H that contains 2-dimensional VO2 sheets, they remain insulating even at the highest accessible pressures. The reduction in dimensionality from planar to linear VO networks reduces the dispersion of the V-O π bands that define the band gap and leads to insulating behavior at all measured pressures.

Exsolution of SrO during the Topochemical Conversion of LaSr3CoRuO8 to the Oxyhydride LaSr3CoRuO4H4.

 Reaction of the n = 1 Ruddlesden-Popper oxide LaSr3CoRuO8 with CaH2 yields the oxyhydride phase LaSr3CoRuO4H4 via a topochemical anion exchange. Close inspection of the X-ray and neutron powder diffraction data in combination with HAADF-STEM images reveals that the nanoparticles of SrO are exsolved from the system during the reaction, with the change in cation stoichiometry accommodated by the inclusion of n > 1 (Co/Ru)nOn+1H2n "perovskite" layers into the Ruddlesden-Popper stacking sequence. This novel pseudotopochemical process offers a new route for the formation of n > 1 Ruddlesden-Popper structured materials. Magnetization data are consistent with a LaSr3Co+Ru2+O4H4 (Co+, d8, S = 1; Ru2+, d6, S = 0) oxidation/spin state combination. Neutron diffraction and µ+SR data show no evidence for long-range magnetic order down to 2 K, suggesting the diamagnetic Ru2+ centers impede the Co-Co magnetic-exchange interactions.

Chemical Pressure-Induced Anion Order-Disorder Transition in LnHO Enabled by Hydride Size Flexibility.

While cation order-disorder transitions have been achieved in a wide range of materials and provide crucial effects in various physical and chemical properties, anion analogues are scarce. Here we have expanded the number of known lanthanide oxyhydrides, LnHO (Ln = La, Ce, Pr, Nd), to include Ln = Sm, Gd, Tb, Dy, Ho, and Er, which has allowed the observation of an anion order-disorder transition from the anion-ordered fluorite structure ( P4/ nmm) for larger Ln3+ ions (La-Nd) to a disordered arrangement ( Fm3̅ m) for smaller Ln3+ (Sm-Er). Structural analysis reveals that with the increase of Ln3+ radius (application of negative chemical pressure), the oxide anion in the disordered phase becomes too under-bonded, which drives a change to an anion-ordered structure, with smaller OLn4 and larger HLn4 tetrahedra, demonstrating that the size flexibility of hydride anions drives this transition. Such anion ordering control is crucial regarding applications that involve hydride diffusion such as catalysis and electrochemical solid devices.

Extreme Sensitivity of a Topochemical Reaction to Cation Substitution: SrVO2H versus SrV1- xTi xO1.5H1.5.

The anion-ordered oxide-hydride SrVO2H is an antiferromagnetic insulator due to strong correlations between vanadium d electrons. In an attempt to hole-dope SrVO2H into a metallic state, a strategy of first preparing SrV1- xTi xO3 phases and then converting them to the corresponding SrV1- xTi xO2H phases via reaction with CaH2 was followed. This revealed that the solid solution between SrVO3 and SrTiO3 is only stable at high temperature. In addition, reactions between SrV0.95Ti0.05O3 and CaH2 were observed to yield SrV0.95Ti0.05O1.5H1.5 not SrV0.95Ti0.05O2H. This dramatic change in reactivity for a very modest change in initial chemical composition is attributed to an electronic destabilization of SrVO2H on titanium substitution. Density functional theory calculations indicate that the presence of an anion-ordered, tetragonal SrMO2H phase is uniquely associated with a d2 electron count and that titanium substitution leads to an electronic destabilization of SrV1- xTi xO2H phases, which, ultimately, drives further reaction of SrV1- xTi xO2H to SrV1- xTi xO1.5H1.5. The observed sensitivity of the reaction products to the chemical composition of initial phases highlights some of the difficulties associated with electronically doping metastable materials prepared by topochemical reactions.

Sr2FeIrO4: Square-Planar Ir(II) in an Extended Oxide.

Topochemical reduction of the double-perovskite oxide Sr2FeIrO6 under dilute hydrogen leads to the formation of Sr2FeIrO4. This phase consists of ordered infinite sheets of apex-linked Fe2+O4 and Ir2+O4 squares stacked with Sr2+ cations and is the first report of Ir2+ in an extended oxide phase. Plane-wave density functional theory calculations indicate high-spin Fe2+ (d6, S = 2) and low-spin Ir2+ (d7, S = 1/2) configurations for the metals and confirm that both ions have a doubly occupied d z2 orbital, a configuration that is emerging as a consistent feature of all layered oxide phases of this type. The stability and double occupation of d z2 in the Ir2+ ions invites a somewhat unexpected analogy to the extensively studied Ir4+ ion as both ions share a common near-degenerate (d xy/ xz/ yz)5 valence configuration. On cooling below 115 K, Sr2FeIrO4 enters a magnetically ordered state in which the Ir and Fe sublattices adopt type II antiferromagnetically coupled networks which interpenetrate each other, leading to frustration in the nearest-neighbor Fe-O-Ir couplings, half of which are ferromagnetic and half antiferromagnetic. The spin frustration drives a symmetry-lowering structural distortion in which the four equivalent Ir-O and Fe-O distances of the tetragonal I4/ mmm lattice split into two mutually trans pairs in a lattice with monoclinic I112/ m symmetry. This strong magneto-lattice coupling arises from the novel local electronic configurations of the Fe2+ and Ir2+ cations and their cation-ordered arrangement in a distorted perovskite lattice.

Doped Sr2FeIrO6-Phase Separation and a Jeff ≠ 0 State for Ir5.

High-resolution synchrotron X-ray and neutron powder diffraction data demonstrate that, in contrast to recent reports, Sr2FeIrO6 adopts an I1̅ symmetry double perovskite structure with an a-b-c- tilting distortion. This distorted structure does not tolerate cation substitution, with low levels of A-site (Ca, Ba, La) or Fe-site (Ga) substitution leading to separation into two phases: a stoichiometric I1̅ phase and a cation-substituted, P21/ n symmetry, a-a-c+ distorted double perovskite phase. Magnetization, neutron diffraction, and 57Fe Mössbauer data show that, in common with Sr2FeIrO6, the cation substituted Sr2- xA xFe1- yGa yIrO6 phases undergo transitions to type-II antiferromagnetically ordered states at TN ∼ 120 K. However, in contrast to stoichiometric Sr2FeIrO6, cation substituted samples exhibit a further magnetic transition at TA ∼ 220 K, which corresponds to the ordering of Jeff ≠ 0 Ir5+ centers in the cation-substituted, P21/ n symmetry, double perovskite phases.