In general, magnetic properties of bulk magnetic materials are independent of the humidity of the environment. To obtain a magnetic material that has humidity-sensitive characteristics, water vapour must penetrate the lattice and act on spin sites. Nanoporous materials composed of metal-assembled complexes may be expected to display some humidity response because materials in this category can show functionalities such as gas storage and molecular recognition. Here, we demonstrate humidity-induced reversible variations in the magnetic properties of cyano-bridged cobalt(II)-manganese(II)-chromium(III) metal assemblies. The observed magnetic humidity response is due to adsorption and desorption of a ligand water molecule on the cobalt ion, which changes cobalt (II) between a 6- and 4-fold coordination geometry and switches the magnetic interaction between ferromagnetic coupling and antiferromagnetic coupling.
Solvent exchange caused reversible variations in color, magnetic properties, and the Faraday spectra of Co(II)(1.5)[Cr(III)(CN)(6)].7.5H2O (1) prepared in water. Compound 1 turned from peach to deep blue, which was due to a change in the coordination geometry on Co(II) ion from six-coordinate pseudo-octahedral (OhCo(II)) to four-coordinate pseudo-tetrahedral (TdCo(II)) geometries, when it was immersed in EtOH. The confirmed formula for the deep blue powder was Co(II)(1.5)[Cr(III)(CN)(6)].2.5H2O.2.0EtOH. The magnetic properties also changed; that is, the magnetic critical temperature, saturation magnetization, and coercive field went from 25 to 18 K, from 7.0 to 5.5 micro(B), and from 240 to 120 G, respectively. This solvatomagnetism is because the ferromagnetic magnetic coupling between OhCo(II) (S = 3/2) and Cr(III) (S = 3/2) is replaced by the antiferromagnetic coupling between TdCo(II) (S = 3/2) and Cr(III) (S = 3/2). Accompanying the solvatochromism and solvatomagnetism, the Faraday spectra drastically changed. The Faraday ellipticity (FE) spectrum of 1 had a distorted dispersive peak (A), which is due to the 4T1g --> 4T1g, 2T1g transitions of OhCo(II) ion, around 480 nm, but the FE spectra of 2 showed a new dispersive-shaped band (B) at 580 nm. The observed B band was assigned to the 4A2 --> 4T2 transition of the TdCo(II) ion. The Faraday spectra were well reproduced by a simulation that considers the ligand field splitting, spin-orbital coupling, and the ferromagnetic ordering. These solvatochromic effects were repeatedly observed.
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Electronic structure of the 3x3 ordered-phase of a silicon (Si) layer on Al(111) has been studied by angle resolved photoemission spectroscopy (ARPES) technique using synchrotron radiation and modeled by a trial atomic model. A closed Fermi surface originating from liniarly dispersing band is identified. A band structure calculation of a trial atomic model of the honeycomb silicene on Al(111) implies that the metallic band originates from the Al-Si hybrid state that has the Dirac cone-like dispersion curves. The Si layer on Al( 111) can be a model system of Xene to realize the massless electronic system through the overlayer-substrate interaction.
1551 Background: Cancer genomic profiling (CGP) tests have been approved in Japan since June 2019, with the requisite that all test results be discussed by molecular tumor boards (MTBs). More than 20,000 patients in over 200 designated hospitals have taken CGP tests by December 2021. As CGP tests have entered clinical practice, streamlining decision making by MTBs and standardizing interpretation of test results and treatment recommendations have become urgent issues. Here, we evaluated the utility of Chrovis, an annotation algorithm for reporting CGP tests to support MTBs make their recommendations. Methods: We retrospectively reviewed the reporting process of all approved CGP tests done at The University of Tokyo Hospital between December 2019 and November 2021. Chrovis provided annotation for each genetic variant by incorporating biologic, clinical, and therapeutic information by referencing several public knowledge databases and using natural language processing, and generated reports using the automated program. The MTB reviewed and made any necessary changes before finalizing the report. Changes in disclosure of germline findings were made according to the recommendations of a national guideline with consideration of past and family history. Results: Of the 243 tests, 91 changes in 81 Chrovis reports (33% of all reports) were made by the MTB. The most common type of change was germline disclosure with 26 changes (29%), followed by clinical trial information in Japan (18 changes, 20%) and recommendation of the patient-proposed national basket trial with multiple targeted agents (17 changes, 19%). Changes in germline disclosure increased from June 2021, when an update to a national guideline was released, while the proportion of changes in the latter two types remained unchanged. Gene alterations that led to the highest number of changes was TP53, with 13 changes. Changes in therapeutic recommendations were frequently observed in the RAS/MAPK pathway ( BRAF, KRAS, NF1, NRAS) with 12 changes. More changes were required with a tumor-only tissue CGP panel (57 of 149) compared with a matched tumor/normal tissue CGP panel (24 of 94, p = 0.04), mostly due to germline disclosure (24 vs. 2 changes). Conclusions: We observed that automated algorithm-based reporting was sufficient in 67% of reports. Recommendation for germline disclosure still requires manual supervision, particularly with tumor-only tissue CGP panels if algorithms do not incorporate medical history. The process of recommending clinical trials needs improvement, e.g., standardizing database formats for inclusion and exclusion criteria.
A cutting edge therapy for future immuno-oncology is targeting a new series of inhibitory receptors (IRs): LAG-3, TIM-3, and TIGIT. Both immunogenomic analyses and diagnostic platforms to distinguish candidates and predict good responders to these IR-related agents are vital in clinical pathology. By applying an automated single-cell count for immunolabeled LAG-3, TIM-3, and TIGIT, we revealed that individual IR levels with exclusive domination in each tumour can be valid biomarkers for profiling human renal cell carcinoma (RCC). We uncovered the immunogenomic landscape associated with individual IR levels in human RCC tumours with metastases in various organs and histological subtypes. We then externally validated our results and devised a workflow with optimal biomarker cut-offs for discriminating the tumour profiles of LAG-3, TIM-3, and TIGIT. The discrimination of LAG-3, TIM-3, and TIGIT profiles in tumours may have a broad impact on investigations on immunotherapy responses after targeting a new series of IRs.
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