Improving the creation of SiV centers in diamond via sub-µs pulsed annealing treatment.

Silicon-vacancy (SiV) centers in diamond are emerging as promising quantum emitters in applications such as quantum communication and quantum information processing. Here, we demonstrate a sub-µs pulsed annealing treatment that dramatically increases the photoluminescence of SiV centers in diamond. Using a silane-functionalized adamantane precursor and a laser-heated diamond anvil cell, the temperature and energy conditions required to form SiV centers in diamond were mapped out via an optical thermometry system with an accuracy of ±50 K and a 1 µs temporal resolution. Annealing scheme studies reveal that pulsed annealing can obviously minimize the migration of SiV centers out of the diamond lattice, and a 2.5-fold increase in the number of emitting centers was achieved using a series of 200-ns pulses at a 50 kHz repetition rate via acousto-optic modulation. Our study provides a novel pulsed annealing treatment approach to improve the efficiency of the creation of SiV centers in diamond.

SMARCAL1 is a dual regulator of innate immune signaling and PD-L1 expression that promotes tumor immune evasion.

Genomic instability can trigger cancer-intrinsic innate immune responses that promote tumor rejection. However, cancer cells often evade these responses by overexpressing immune checkpoint regulators, such as PD-L1. Here, we identify the SNF2-family DNA translocase SMARCAL1 as a factor that favors tumor immune evasion by a dual mechanism involving both the suppression of innate immune signaling and the induction of PD-L1-mediated immune checkpoint responses. Mechanistically, SMARCAL1 limits endogenous DNA damage, thereby suppressing cGAS-STING-dependent signaling during cancer cell growth. Simultaneously, it cooperates with the AP-1 family member JUN to maintain chromatin accessibility at a PD-L1 transcriptional regulatory element, thereby promoting PD-L1 expression in cancer cells. SMARCAL1 loss hinders the ability of tumor cells to induce PD-L1 in response to genomic instability, enhances anti-tumor immune responses and sensitizes tumors to immune checkpoint blockade in a mouse melanoma model. Collectively, these studies uncover SMARCAL1 as a promising target for cancer immunotherapy.

Ultrafast x-ray detection of low-spin iron in molten silicate under deep planetary interior conditions.

The spin state of Fe can alter the key physical properties of silicate melts, affecting the early differentiation and the dynamic stability of the melts in the deep rocky planets. The low-spin state of Fe can increase the affinity of Fe for the melt over the solid phases and the electrical conductivity of melt at high pressures. However, the spin state of Fe has never been measured in dense silicate melts due to experimental challenges. We report detection of dominantly low-spin Fe in dynamically compressed olivine melt at 150 to 256 gigapascals and 3000 to 6000 kelvin using laser-driven shock wave compression combined with femtosecond x-ray diffraction and x-ray emission spectroscopy using an x-ray free electron laser. The observation of dominantly low-spin Fe supports gravitationally stable melt in the deep mantle and generation of a dynamo from the silicate melt portion of rocky planets.

Quasi-One-Dimensional Metallicity in Compressed CsSnI3.

Low-dimensional metal halides exhibit strong structural and electronic anisotropies, making them candidates for accessing unusual electronic properties. Here, we demonstrate pressure-induced quasi-one-dimensional (quasi-1D) metallicity in δ-CsSnI3. With the application of pressure up to 40 GPa, the initially insulating δ-CsSnI3 transforms to a metallic state. Synchrotron X-ray diffraction and Raman spectroscopy indicate that the starting 1D chain structure of edge-sharing Sn-I octahedra in δ-CsSnI3 is maintained in the high-pressure metallic phase while the SnI6 octahedral chains are distorted. Our experiments combined with first-principles density functional theory calculations reveal that pressure induces Sn-Sn hybridization and enhances Sn-I coupling within the chain, leading to band gap closure and formation of conductive SnI6 distorted octahedral chains. In contrast, the interchain I...I interactions remain minimal, resulting in a highly anisotropic electronic structure and quasi-1D metallicity. Our study offers a high-pressure approach for achieving diverse electronic platforms in the broad family of low-dimensional metal halides.

Overcoming current challenges to T-cell receptor therapy via metabolic targeting to increase antitumor efficacy, durability, and tolerability.

The antitumor potential of personalized immunotherapy, including adoptive T-cell therapy, has been shown in both preclinical and clinical studies. Combining cell therapy with targeted metabolic interventions can further enhance therapeutic outcomes in terms of magnitude and durability. The ability of a T cell receptor to recognize peptides derived from tumor neoantigens allows for a robust yet specific response against cancer cells while sparing healthy tissue. However, there exist challenges to adoptive T cell therapy such as a suppressive tumor milieu, the fitness and survival of transferred cells, and tumor escape, all of which can be targeted to further enhance the antitumor potential of T cell receptor-engineered T cell (TCR-T) therapy. Here, we explore current strategies involving metabolic reprogramming of both the tumor microenvironment and the cell product, which can lead to increased T cell proliferation, survival, and anti-tumor cytotoxicity. In addition, we highlight potential metabolic pathways and targets which can be leveraged to improve engraftment of transferred cells and obviate the need for lymphodepletion, while minimizing off-target effects. Metabolic signaling is delicately balanced, and we demonstrate the need for thoughtful and precise interventions that are tailored for the unique characteristics of each tumor. Through improved understanding of the interplay between immunometabolism, tumor resistance, and T cell signaling, we can improve current treatment regimens and open the door to potential synergistic combinations.

Cesium-mediated electron redistribution and electron-electron interaction in high-pressure metallic CsPbI3.

Electron-phonon coupling was believed to govern the carrier transport in halide perovskites and related phases. Here we demonstrate that electron-electron interaction enhanced by Cs-involved electron redistribution plays a direct and prominent role in the low-temperature electrical transport of compressed CsPbI3 and renders Fermi liquid (FL)-like behavior. By compressing δ-CsPbI3 to 80 GPa, an insulator-semimetal-metal transition occurs, concomitant with the completion of a slow structural transition from the one-dimensional Pnma (δ) phase to a three-dimensional Pmn21 (ε) phase. Deviation from FL behavior is observed upon CsPbI3 entering the metallic ε phase, which progressively evolves into a FL-like state at 186 GPa. First-principles density functional theory calculations reveal that the enhanced electron-electron coupling results from the sudden increase of the 5d state occupation in Cs and I atoms. Our study presents a promising strategy of cationic manipulation for tuning the electronic structure and carrier scattering of halide perovskites at high pressure.

Tuning Defects in a Halide Double Perovskite with Pressure.

Dopant defects in semiconductors can trap charge carriers or ionize to produce charge carriers─playing a critical role in electronic transport. Halide perovskites are a technologically important semiconductor family with a large pressure response. Yet, to our knowledge, the effect of high pressures on defects in halide perovskites has not been experimentally investigated. Here, we study the structural, optical, and electronic consequences of compressing the small-bandgap double perovskites Cs2AgTlX6 (X = Cl or Br) up to 56 GPa. Mild compression to 1.7 GPa increases the conductivity of Cs2AgTlBr6 by ca. 1 order of magnitude and decreases its bandgap from 0.94 to 0.7 eV. Subsequent compression yields complex optoelectronic behavior: the bandgap varies by 1.2 eV and conductivity ranges by a factor of 104. These conductivity changes cannot be explained by the evolving bandgap. Instead, they can be understood as tuning of the bromine vacancy defect with pressure─varying between a delocalized shallow defect state with a small ionization energy and a localized deep defect state with a large ionization energy. Activation energy measurements reveal that the shallow-to-deep defect transition occurs near 1.5 GPa, well before the cubic-to-tetragonal phase transition. An analysis of the orbital interactions in Cs2AgTlBr6 illustrates how the bromine vacancy weakens the adjacent Tl s-Br p antibonding interaction, driving the shallow-to-deep defect transition. Our orbital analysis leads us to propose that halogen vacancies are most likely to be shallow donors in halide double perovskites that have a conduction band derived from the octahedral metal's s orbitals.

Preservation of high-pressure volatiles in nanostructured diamond capsules.

High pressure induces dramatic changes and novel phenomena in condensed volatiles1,2 that are usually not preserved after recovery from pressure vessels. Here we report a process that pressurizes volatiles into nanopores of type 1 glassy carbon precursors, converts glassy carbon into nanocrystalline diamond by heating and synthesizes free-standing nanostructured diamond capsules (NDCs) capable of permanently preserving volatiles at high pressures, even after release back to ambient conditions for various vacuum-based diagnostic probes including electron microscopy. As a demonstration, we perform a comprehensive study of a high-pressure argon sample preserved in NDCs. Synchrotron X-ray diffraction and high-resolution transmission electron microscopy show nanometre-sized argon crystals at around 22.0 gigapascals embedded in nanocrystalline diamond, energy-dispersive X­ray spectroscopy provides quantitative compositional analysis and electron energy-loss spectroscopy details the chemical bonding nature of high-pressure argon. The preserved pressure of the argon sample inside NDCs can be tuned by controlling NDC synthesis pressure. To test the general applicability of the NDC process, we show that high-pressure neon can also be trapped in NDCs and that type 2 glassy carbon can be used as the precursor container material. Further experiments on other volatiles and carbon allotropes open the possibility of bringing high-pressure explorations on a par with mainstream condensed-matter investigations and applications.

Making the most of metastability.

Researchers seek to preserve materials that are formed at high pressure.

Engineering Bright and Mechanosensitive Alkaline-Earth Rare-Earth Upconverting Nanoparticles.

Upconverting nanoparticles (UCNPs) are an emerging platform for mechanical force sensing at the nanometer scale. An outstanding challenge in realizing nanometer-scale mechano-sensitive UCNPs is maintaining a high mechanical force responsivity in conjunction with bright optical emission. This Letter reports mechano-sensing UCNPs based on the lanthanide dopants Yb3+ and Er3+, which exhibit a strong ratiometric change in emission spectra and bright emission under applied pressure. We synthesize and analyze the pressure response of five different types of nanoparticles, including cubic NaYF4 host nanoparticles and alkaline-earth host materials CaLuF, SrLuF, SrYbF, and BaLuF, all with lengths of 15 nm or less. By combining optical spectroscopy in a diamond anvil cell with single-particle brightness, we determine the noise equivalent sensitivity (GPa/√Hz) of these particles. The SrYb0.72Er0.28F@SrLuF particles exhibit an optimum noise equivalent sensitivity of 0.26 ± 0.04 GPa/√Hz. These particles present the possibility of robust nanometer-scale mechano-sensing.

Femtosecond Visualization of hcp-Iron Strength and Plasticity under Shock Compression.

Iron is a key constituent of planets and an important technological material. Here, we combine in situ ultrafast x-ray diffraction with laser-induced shock compression experiments on Fe up to 187(10) GPa and 4070(285) K at 10^{8} s^{-1} in strain rate to study the plasticity of hexagonal-close-packed (hcp)-Fe under extreme loading states. {101[over ¯]2} deformation twinning controls the polycrystalline Fe microstructures and occurs within 1 ns, highlighting the fundamental role of twinning in hcp polycrystals deformation at high strain rates. The measured deviatoric stress initially increases to a significant elastic overshoot before the onset of flow, attributed to a slower defect nucleation and mobility. The initial yield strength of materials deformed at high strain rates is thus several times larger than their longer-term flow strength. These observations illustrate how time-resolved ultrafast studies can reveal distinctive plastic behavior in materials under extreme environments.

Evidence for oxygenation of Fe-Mg oxides at mid-mantle conditions and the rise of deep oxygen.

As the reaction product of subducted water and the iron core, FeO2 with more oxygen than hematite (Fe2O3) has been recently recognized as an important component in the D" layer just above the Earth's core-mantle boundary. Here, we report a new oxygen-excess phase (Mg, Fe)2O3+ δ (0 < δ < 1, denoted as 'OE-phase'). It forms at pressures greater than 40 gigapascal when (Mg, Fe)-bearing hydrous materials are heated over 1500 kelvin. The OE-phase is fully recoverable to ambient conditions for ex situ investigation using transmission electron microscopy, which indicates that the OE-phase contains ferric iron (Fe3+) as in Fe2O3 but holds excess oxygen through interactions between oxygen atoms. The new OE-phase provides strong evidence that H2O has extraordinary oxidation power at high pressure. Unlike the formation of pyrite-type FeO2Hx which usually requires saturated water, the OE-phase can be formed with under-saturated water at mid-mantle conditions, and is expected to be more ubiquitous at depths greater than 1000 km in the Earth's mantle. The emergence of oxygen-excess reservoirs out of primordial or subducted (Mg, Fe)-bearing hydrous materials may revise our view on the deep-mantle redox chemistry.

Mineralogy of the deep lower mantle in the presence of H2O.

Understanding the mineralogy of the Earth's interior is a prerequisite for unravelling the evolution and dynamics of our planet. Here, we conducted high pressure-temperature experiments mimicking the conditions of the deep lower mantle (DLM, 1800-2890 km in depth) and observed surprising mineralogical transformations in the presence of water. Ferropericlase, (Mg, Fe)O, which is the most abundant oxide mineral in Earth, reacts with H2O to form a previously unknown (Mg, Fe)O2H x (x ≤ 1) phase. The (Mg, Fe)O2H x has a pyrite structure and it coexists with the dominant silicate phases, bridgmanite and post-perovskite. Depending on Mg content and geotherm temperatures, the transformation may occur at 1800 km for (Mg0.6Fe0.4)O or beyond 2300 km for (Mg0.7Fe0.3)O. The (Mg, Fe)O2H x is an oxygen excess phase that stores an excessive amount of oxygen beyond the charge balance of maximum cation valences (Mg2+, Fe3+ and H+). This important phase has a number of far-reaching implications including extreme redox inhomogeneity, deep-oxygen reservoirs in the DLM and an internal source for modulating oxygen in the atmosphere.

Probing the Electronic Band Gap of Solid Hydrogen by Inelastic X-Ray Scattering up to 90 GPa.

Metallization of hydrogen as a key problem in modern physics is the pressure-induced evolution of the hydrogen electronic band from a wide-gap insulator to a closed gap metal. However, due to its remarkably high energy, the electronic band gap of insulating hydrogen has never before been directly observed under pressure. Using high-brilliance, high-energy synchrotron radiation, we developed an inelastic x-ray probe to yield the hydrogen electronic band information in situ under high pressures in a diamond-anvil cell. The dynamic structure factor of hydrogen was measured over a large energy range of 45 eV. The electronic band gap was found to decrease linearly from 10.9 to 6.57 eV, with an 8.6 times densification (ρ/ρ_{0}∼8.6) from zero pressure up to 90 GPa.

Preserving a robust CsPbI3 perovskite phase via pressure-directed octahedral tilt.

Functional CsPbI3 perovskite phases are not stable at ambient conditions and spontaneously convert to a non-perovskite δ phase, limiting their applications as solar cell materials. We demonstrate the preservation of a black CsPbI3 perovskite structure to room temperature by subjecting the δ phase to pressures of 0.1 - 0.6 GPa followed by heating and rapid cooling. Synchrotron X-ray diffraction and Raman spectroscopy indicate that this perovskite phase is consistent with orthorhombic γ-CsPbI3. Once formed, γ-CsPbI3 could be then retained after releasing pressure to ambient conditions and shows substantial stability at 35% relative humidity. First-principles density functional theory calculations indicate that compression directs the out-of-phase and in-phase tilt between the [PbI6]4- octahedra which in turn tune the energy difference between δ- and γ-CsPbI3, leading to the preservation of γ-CsPbI3. Here, we present a high-pressure strategy for manipulating the (meta)stability of halide perovskites for the synthesis of desirable phases with enhanced materials functionality.

Differential Immune Modulation With Carbon-Ion Versus Photon Therapy.

PURPOSE: Radiation therapy (RT) modulates the immune characteristics of the tumor microenvironment (TME). It is not known whether these effects are dependent on the type of RT used. METHODS AND MATERIALS: We evaluated the immunomodulatory effects of carbon-ion therapy (CiRT) compared with biologically equivalent doses of photon therapy (PhRT) on solid tumors. Orthotopic 4T1 mammary tumors in immunocompetent hosts were treated with CiRT or biologically equivalent doses of PhRT. Seventy-two hours after RT, tumors were harvested and the immune characteristics of the TME were quantified by flow cytometry and multiplex cytokine analyses. RESULTS: PhRT decreased the abundance of CD4+ and CD8+ T cells in the TME at all doses tested, with compensatory increases in proliferation. By contrast, CiRT did not significantly alter CD8+ T-cell infiltration. High-dose CiRT increased secretion of proinflammatory cytokines by tumor-infiltrating CD8+ T cells, including granzyme B, IL-2, and TNF-α, with no change in IFN-γ. Conversely, high-dose PhRT increased CD8+ T-cell secretion of IFN-γ only. At most of the doses studied, PhRT increased proliferation of immunosuppressive regulatory T cells; this was only seen with high-dose CiRT. Cytokine analyses of bulk dissociated tumors showed that CiRT significantly increased levels of IFN-γ, IL-2, and IL-1ß, whereas PhRT increased IL-6 levels alone. CONCLUSIONS: At low doses, lymphocytes differ in their sensitivity to CiRT compared with PhRT. Unlike PhRT, low-dose CiRT is generally lymphocyte-sparing. At higher doses, CiRT is a more potent inducer of proinflammatory cytokines and merits further study as a modulator of the immunologic characteristics of the TME.

Revealing Local Disorder in a Silver-Bismuth Halide Perovskite upon Compression.

The halide double perovskite Cs2AgBiBr6 has emerged as a promising nontoxic alternative to the lead halide perovskites APbX3 (A = organic cation or Cs; X = I or Br). Here, we perform high-pressure synchrotron X-ray total scattering on Cs2AgBiBr6 and discover local disorder that is hidden from conventional Bragg analysis. While our powder diffraction data show that the average structure remains cubic up to 2.1 GPa, analysis of the X-ray pair distribution function reveals that the local structure is better described by a monoclinic space group, with significant distortion within the Ag-Br and Bi-Br octahedra and off-centering of the Cs atoms. By tracking the distribution of interatomic Cs-Br distances, we find that the local disorder is enhanced upon compression, and we corroborate these results with molecular dynamics simulations. The observed local disorder affords new understanding of this promising material and potentially offers a new parameter to tune in halide perovskite lattices.

Blocking IL1 Beta Promotes Tumor Regression and Remodeling of the Myeloid Compartment in a Renal Cell Carcinoma Model: Multidimensional Analyses.

PURPOSE: Intratumoral immunosuppression mediated by myeloid-derived suppressor cells (MDSC) and tumor-associated macrophages (TAM) represents a potential mechanism of immune checkpoint inhibitor (ICI) resistance in solid tumors. By promoting TAM and MDSC infiltration, IL1ß may drive adaptive and innate immune resistance in renal cell carcinoma (RCC) and in other tumor types. EXPERIMENTAL DESIGN: Using the RENCA model of RCC, we evaluated clinically relevant combinations of anti-IL1ß plus either anti-PD-1 or the multitargeted tyrosine kinase inhibitor (TKI), cabozantinib. We performed comprehensive immune profiling of established RENCA tumors via multiparameter flow cytometry, tumor cytokine profiling, and single-cell RNA sequencing (RNA-seq). Similar analyses were extended to the MC38 tumor model. RESULTS: Analyses via multiparameter flow cytometry, tumor cytokine profiling, and single-cell RNA-seq showed that anti-IL1ß reduces infiltration of polymorphonuclear MDSCs and TAMs. Combination treatment with anti-IL1ß plus anti-PD-1 or cabozantinib showed increased antitumor activity that was associated with decreases in immunosuppressive MDSCs and increases in M1-like TAMs. CONCLUSIONS: Single-cell RNA-seq analyses show that IL1ß blockade and ICI or TKI remodel the myeloid compartment through nonredundant, relatively T-cell-independent mechanisms. IL1ß is an upstream mediator of adaptive myeloid resistance and represents a potential target for kidney cancer immunotherapy.

Synthesis of Atomically Thin Hexagonal Diamond with Compression.

Atomically thin diamond, also called diamane, is a two-dimensional carbon allotrope and has attracted considerable scientific interest because of its potential physical properties. However, the successful synthesis of a pristine diamane has up until now not been achieved. We demonstrate the realization of a pristine diamane through diamondization of mechanically exfoliated few-layer graphene via compression. Resistance, optical absorption, and X-ray diffraction measurements reveal that hexagonal diamane (h-diamane) with a bandgap of 2.8 ± 0.3 eV forms by compressing trilayer and thicker graphene to above 20 GPa at room temperature and can be preserved upon decompression to ∼1.0 GPa. Theoretical calculations indicate that a (-2110)-oriented h-diamane is energetically stable and has a lower enthalpy than its few-layer graphene precursor above the transition pressure. Compared to gapless graphene, semiconducting h-diamane offers exciting possibilities for carbon-based electronic devices.

Nitrogen in black phosphorus structure.

Group V elements in crystal structure isostructural to black phosphorus with unique puckered two-dimensional layers exhibit exciting physical and chemical phenomena. However, as the first element of group V, nitrogen has never been found in the black phosphorus structure. Here, we report the synthesis of the black phosphorus-structured nitrogen at 146 GPa and 2200 K. Metastable black phosphorus-structured nitrogen was retained after quenching it to room temperature under compression and characterized in situ during decompression to 48 GPa, using synchrotron x-ray diffraction and Raman spectroscopy. We show that the original molecular nitrogen is transformed into extended single-bonded structure through gauche and trans conformations. Raman spectroscopy shows that black phosphorus-structured nitrogen is strongly anisotropic and exhibits high Raman intensities in two A g normal modes. Synthesis of black phosphorus-structured nitrogen provides a firm base for exploring new type of high-energy-density nitrogen and a new direction of two-dimensional nitrogen.