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Transition metal takes charge The introduction of 'foreign' elements into transition-metal oxides (called chemical doping) can change the valence state of the metal's cations and hence modify the physical properties of the material as a whole. These changes can be dramatic, for example causing high-temperature superconductivity in copper oxides and colossal magnetoresistance in manganese oxides. Youwen Long et al . have identified an oxide system, the perovskite LaCu 3 Fe 4 O 12 , in which changes in valence state occur when charge is shuffled between different cations (iron and copper) in the host structure, rather than via doping. As a result, the material can be reversibly transformed from one possessing iron in an unusually high Fe 3.75+ state (partnered with fairly common Cu 2+ ions) to one possessing rare Cu 3+ ions. These changes are reflected in the magnetic and electronic properties of the material and, intriguingly, the material contracts slightly on being warmed through the transition. The temperature sensitivity of this effect makes it a strong candidate for technological applications. This paper identifies an oxide system where changes in valence state occur as a result of charge being shuffled between different cations in the host structure, rather than via doping, this charge transfer being sensitive to temperature. As a result, the material can be reversibly transformed from one possessing iron in an unusually high Fe3.75+ state to one possessing rare Cu3+ ions. These changes are reflected in the magnetic and electronic properties of the material and, intriguingly, are accompanied by negative thermal expansion. Changes of valence states in transition-metal oxides often cause significant changes in their structural and physical properties 1 , 2 . Chemical doping is the conventional way of modulating these valence states. In ABO 3 perovskite and/or perovskite-like oxides, chemical doping at the A site can introduce holes or electrons at the B site, giving rise to exotic physical properties like high-transition-temperature superconductivity and colossal magnetoresistance 3 , 4 . When valence-variable transition metals at two different atomic sites are involved simultaneously, we expect to be able to induce charge transfer—and, hence, valence changes—by using a small external stimulus rather than by introducing a doping element. Materials showing this type of charge transfer are very rare, however, and such externally induced valence changes have been observed only under extreme conditions like high pressure 5 , 6 . Here we report unusual temperature-induced valence changes at the A and B sites in the A-site-ordered double perovskite LaCu 3 Fe 4 O 12 ; the underlying intersite charge transfer is accompanied by considerable changes in the material’s structural, magnetic and transport properties. When cooled, the compound shows a first-order, reversible transition at 393 K from LaCu 2+ 3 Fe 3.75+ 4 O 12 with Fe 3.75+ ions at the B site to LaCu 3+ 3 Fe 3+ 4 O 12 with rare Cu 3+ ions at the A site. Intersite charge transfer between the A-site Cu and B-site Fe ions leads to paramagnetism-to-antiferromagnetism and metal-to-insulator isostructural phase transitions. What is more interesting in relation to technological applications is that this above-room-temperature transition is associated with a large negative thermal expansion.

Scanning tunnelling microscopy images of the evolution of the pseudogap phase of a hole-doped cuprate superconductor suggest that it emerges in localized clusters that grow with increasing doping. Moreover, the eventual coalescence of these clusters coincides with the emergence of superconductivity. Superconductivity emerges from the cuprate antiferromagnetic Mott state with hole doping. The resulting electronic structure 1 is not understood, although changes in the state of oxygen atoms seem paramount 2 , 3 , 4 , 5 . Hole doping first destroys the Mott state, yielding a weak insulator 6 , 7 where electrons localize only at low temperatures without a full energy gap. At higher doping levels, the ‘pseudogap’, a weakly conducting state with an anisotropic energy gap and intra-unit-cell breaking of 90° rotational (C 4v ) symmetry, appears 3 , 4 , 8 , 9 , 10 . However, a direct visualization of the emergence of these phenomena with increasing hole density has never been achieved. Here we report atomic-scale imaging of electronic structure evolution from the weak insulator through the emergence of the pseudogap to the superconducting state in Ca 2− x Na x CuO 2 Cl 2 . The spectral signature of the pseudogap emerges at the lowest doping level from a weakly insulating but C 4v -symmetric matrix exhibiting a distinct spectral shape. At slightly higher hole density, nanoscale regions exhibiting pseudogap spectra and 180° rotational (C 2v ) symmetry form unidirectional clusters within the C 4v -symmetric matrix. Thus, hole doping proceeds by the appearance of nanoscale clusters of localized holes within which the broken-symmetry pseudogap state is stabilized. A fundamentally two-component electronic structure 11 then exists in Ca 2− x Na x CuO 2 Cl 2 until the C 2v -symmetric clusters touch at higher doping levels, and the long-range superconductivity appears.

Removing electrons from the CuO₂ plane of cuprates alters the electronic correlations sufficiently to produce high-temperature superconductivity. Associated with these changes are spectral-weight transfers from the high-energy states of the insulator to low energies. In theory, these should be detectable as an imbalance between the tunneling rate for electron injection and extraction--a tunneling asymmetry. We introduce atomic-resolution tunneling-asymmetry imaging, finding virtually identical phenomena in two lightly hole-doped cuprates: Ca₁.₈₈Na₀.₁₂CuO₂Cl₂ and Bi₂Sr₂Dy₀.₂Ca₀.₈Cu₂O₈₊δ. Intense spatial variations in tunneling asymmetry occur primarily at the planar oxygen sites; their spatial arrangement forms a Cu-O-Cu bond-centered electronic pattern without long-range order but with 4a₀-wide unidirectional electronic domains dispersed throughout (a₀: the Cu-O-Cu distance). The emerging picture is then of a partial hole localization within an intrinsic electronic glass evolving, at higher hole densities, into complete delocalization and highest-temperature superconductivity.

High-transition-temperature (high- T c ) superconductivity is ubiquitous in the cuprates containing CuO 2 planes, but each cuprate has its own character. The study of the material dependence of the d -wave superconducting gap (SG) should provide important insights into the mechanism of high- T c superconductivity. However, because of the ‘pseudogap’ phenomenon, it is often unclear whether the energy gaps observed by spectroscopic techniques really represent the SG. Here, we use scanning tunnelling spectroscopy to image nearly optimally doped Ca 2− x Na x CuO 2 Cl 2 (Na-CCOC) with T c =25–28 K. It enables us to observe the quasiparticle interference effect in this material, through which we obtain unambiguous information on the SG. Our analysis of quasiparticle interference in Na-CCOC reveals that the SG dispersion near the gap node is almost identical to that of Bi 2 Sr 2 CaCu 2 O y (Bi2212) at the same doping level, despite the T c of Bi2212 being three times higher than that of Na-CCOC. We also find that the SG in Na-CCOC is confined in narrower energy and momentum ranges than Bi2212, which explains—at least in part—the remarkable material dependence of T c .

The PD-1/B7-H1 pathway regulates immune responses and maintains homeostasis. Here, we identified a unique expression of B7 homolog 1 (B7-H1) on masticatory mucosae in the oral cavity. B7-H1 was physiologically expressed on the dorsal surface of the tongue, gingiva, and hard palate. Other squamous epithelia and other structures of the epithelia did not express B7-H1 in the steady state. Physiological B7-H1 expression on masticatory mucosae was limited on prickle cells, and its expression on basal keratinocytes (KCs) was strictly regulated. B7-H1 on prickle cells was upregulated by external topical stimuli, but B7-H1 on basal KCs was induced only by internal stimuli via infiltrating cells. The blocking of KC-associated B7-H1 or the lack of programmed cell death-1 (PD-1) on tissue effector CD4+ T cells in mice lacking B7-H1 on immune cells drastically exacerbated the tissue inflammation induced by topical OVA painting as an exogenous antigen, indicating direct interaction with KCs and CD4+ T cells. Trans-coinhibitory signals by KCs may modulate local T-cell/dendritic cell activation, resulting in inhibition of T-cell responses in both peripheral and secondary lymphoid tissues. Careful control of B7-H1 induction in KCs may play a crucial role in the protection from CD4+ T cell-mediated tissue inflammation by exogenous antigens delivered from the mucosal surface.

The phase diagram of hole-doped copper oxides shows four different electronic phases existing at zero temperature. Familiar among these are the Mott insulator, high-transition-temperature superconductor and metallic phases. A fourth phase, of unknown identity, occurs at light doping along the zero-temperature bound of the ‘pseudogap’ regime 1 . This regime is rich in peculiar electronic phenomena 1 , prompting numerous proposals that it contains some form of hidden electronic order. Here we present low-temperature electronic structure imaging studies of a lightly hole-doped copper oxide: Ca 2- x Na x CuO 2 Cl 2 . Tunnelling spectroscopy (at energies | E | > 100 meV) reveals electron extraction probabilities greatly exceeding those for injection, as anticipated for a doped Mott insulator. However, for | E | < 100 meV, the spectrum exhibits a V-shaped energy gap centred on E = 0. States within this gap undergo intense spatial modulations, with the spatial correlations of a four CuO 2 -unit-cell square ‘checkerboard’, independent of energy. Intricate atomic-scale electronic structure variations also exist within the checkerboard. These data are consistent with an unanticipated crystalline electronic state, possibly the hidden electronic order, existing in the zero-temperature pseudogap regime of Ca 2- x Na x CuO 2 Cl 2 .

When electrons pair in a superconductor, quasi-particles develop an acute sensitivity to different types of scattering potential that is described by the appearance of coherence factors in the scattering amplitudes. Although the effects of coherence factors are well established in isotropic superconductors, they are much harder to detect in their anisotropic counterparts, such as high-superconducting-transition-temperature cuprates. We demonstrate an approach that highlights the momentum-dependent coherence factors in Ca₂₋xNaxCuO₂Cl₂. We used Fourier-transform scanning tunneling spectroscopy to reveal a magnetic-field dependence in quasi-particle scattering interference patterns that is sensitive to the sign of the anisotropic gap. This result is associated with the d-wave coherence factors and quasi-particle scattering off vortices. Our technique thus provides insights into the nature of electron pairing as well as quasi-particle scattering processes in unconventional superconductors.

Understanding the role of competing states in the cuprates is essential for developing a theory for high-temperature superconductivity. We report angle-resolved photoemission spectroscopy experiments which probe the 4a0 x 4a0 charge-ordered state discovered by scanning tunneling microscopy in the lightly doped cuprate superconductor Ca2-xNaxCuO2Cl2. Our measurements reveal a marked dichotomy between the real- and momentum-space probes, for which charge ordering is emphasized in the tunneling measurements and photoemission is most sensitive to excitations near the node of the d-wave superconducting gap. These results emphasize the importance of momentum anisotropy in determining the complex electronic properties of the cuprates and places strong constraints on theoretical models of the charge-ordered state.

Purpose Decreased zinc levels in the macula are reported in patients with age-related macular degeneration, and the zinc chelator N,N,N',N′-tetrakis (2- pyridylmethyl) ethylenediamine) (TPEN) causes death of human retinal pigment epithelial (RPE) cells. The purpose of the present study was to investigate signal transduction pathways during cell death initiated by TPEN, using monkey RPE cells. Methods RPE cells were cultured with TPEN. Activation of calpains and caspases, and proteolysis of their substrates were detected by immunoblotting. Incubation of calpain inhibitor SNJ-1945 or caspase inhibitor z-VAD-fmk was used to confirm activation of specific proteases. Results TPEN caused a time-dependent decrease in viable RPE cells. Cell death was accompanied by activation of calpain-1, caspase-9, and caspase-3. SNJ-1945 inhibited calpain activation and slightly inhibited caspase-9 activation. z-VAD-fmk inhibited caspases and calpain-1 activation. TPEN did not activate caspase-12. Conclusions Relative zinc deficiency in RPE cells causes activation of cytosolic calpain and mitochondrial caspase pathways without ER stress.