773 research outputs found

    Somatic mutation-associated risk index based on lncRNA expression for predicting prognosis in acute myeloid leukemia

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    Objectives: Genomic instability has several implications for acute myeloid leukemia (AML) prognosis. This article aims to construct a somatic mutation-associated risk index (SMRI) of genomic instability for AML to predict prognosis and explore the potential determinants of AML prognosis. Methods: We obtained differentially expressed lncRNAs from genomic instability subtypes and selected six lncRNAs to construct the SMRI through multivariate Cox regression analysis. The median SMRI classified patients into high and low SMRI groups. Kaplan–Meier survival analysis was used to clarify the prognostic differences of SMRI subtypes. Receiver operating characteristic curve analysis was performed to elucidate the value of SMRI as a prognostic indicator. Gene set variation analysis, tumor mutation burden (TMB) analysis, immune infiltration, and immune checkpoint expression analysis were performed to investigate possible causes for the differences in prognosis of SMRI subtypes. Results: The high SMRI group exhibited a poor prognosis, which was characterized by elevated levels of TMB, mutation counts (TP53, NPM1, DNMT3A, and FLT3-TKD), CD8+ T cell infiltration, and immune checkpoint (PD-1, PD-L2, CTLA4, LAG3) expression. The SMRI was still associated with prognosis, even after adjustment for age, sex, cytogenetic risk, DNMT3A status, FLT3 status, and NPM1 status. Gene set variation analysis showed that AML with FLT3-ITD mutation, CEBPA mutation, and LSCs (leukemia stem cells) were enriched in the high SMRI group. Conclusion: Our research suggests that the SMRI derived from genomic instability subtypes is a useful biomarker for predicting prognosis and may be beneficial for improving the clinical outcome of patients with AML.</p

    Experimental and Theoretical Evidence for the Formation of Zinc Tricarbonyl in Solid Argon

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    Zinc carbonyls are extremely rare. Here we report experimental and theoretical evidence of unprecedented zinc tricarbonyl, Zn(CO)3, the next member of the series of 18-electron metal carbonyls Cr(CO)6 → Fe(CO)5 → Ni(CO)4, whereas there is no evidence for the formation of the zinc mono- and dicarbonyls Zn(CO)n (n = 1, 2). DFT calculations predict that the Zn(CO)3 molecule has a singlet ground state with D3h symmetry. The formation of Zn(CO)3 involves 4s → 4p promotion of the Zn atom, which increases the Zn−CO bonding by decreasing the σ repulsion and significantly increasing the Zn 4sp hybrid orbitals → CO π* back-donation

    Observation of Anomalous C−O Bond Weakening on Discandium and Activation Process to CO Dissociation

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    Sc2[η2(μ2-C,O)], the first homoleptic dinuclear metal carbonyl with an unprecedented bridging and side-on-bonded CO, generated from the reaction of laser-ablated Sc atoms with CO in a solid argon matrix, exhibits an unusually low C−O stretching frequency at 1193.4 cm-1, characteristic of an anomalously weakened C−O bond. This CO-activated molecule undergoes ultraviolet−visible photoinduced rearrangement to the CO-dissociated molecule, c-Sc2(μ-C)(μ-O). The infrared absorptions of the new molecules are accurately predicted by quantum chemical calculations, and the activation energy for the isomerization of Sc2[η2(μ2-C, O)] to c-Sc2(μ-C)(μ-O) is calculated to be 15.10 kcal/mol. Our experimental and theoretical results schematically depict an activation process to CO dissociation

    Investigation of Flexible Organic Ligands in the Molybdate System: Delicate Influence of a Peripheral Cluster Environment on the Isopolymolybdate Frameworks

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    By introducing the flexible 1,4-bis(1,2,4-triazol-1-ylmethyl)benzene (L1) and 1,4-bis(imidazole-1-ylmethyl)benzene (L2) ligands into the molybdate system under hydrothermal conditions, 12 novel isopolymolybdate frameworks were obtained: [CuL1(H2O)][Mo3O10] (1), [ML1(H2O)2][Mo3O10] [M = Cu (2), Zn (3), and Co (4)], [Cu2(L1)4][θ-Mo8O26] (5), [Cu4(L1)4][β-Mo8O26]0.5[γ-Mo8O26]0.5·H2O (6), [Ag4(L1)2][β-Mo8O26] (7), [M2(L1)3(H2O)4][β-Mo8O26]·2H2O [M = Zn (8), Co (9), and Ni (10)], and [M4(L2)4][δ-Mo8O26] [M = Cu (11) and Ag (12)]. Compound 1 and isostructural compounds 2−4 exhibit similar three-dimensional (3D) pillar-layered structures. Compound 5 shows a novel pillar-layered framework constructed from two sorts of [CuL1]n left- and right-handed helical chains and the θ-[Mo8O26]4− polyoxoanion. Compound 6 contains two sorts of isomers of β-[Mo8O26]4− and γ-[Mo8O26]4− coexisting in one structure, which induce the formation of two sorts of ladderlike building blocks and finally the polythread structure. The cationic and anionic fragments in compound 7, the dinuclear molecular loop of [Ag2(L1)2]2+ and β-[Mo8O26]4−, are both linked up by single Ag ions, forming two kinds of infinite chains of [Ag3(L1)2]n3n+ and [Ag-β-Mo8O26]n3n−, respectively. Compounds 8−10 are isostructural and exhibit the parallel two-fold (2D→2D) interpenetrated networks based on the β-[Mo8O26]4− cluster. Isostructural compounds 11 and 12 have 3D polythread penetrated frameworks based on the δ-[Mo8O26]4− polyoxoanion. The luminescent properties of the ligands and complexes 3, 6−8, and 11−12 are investigated in the solid state

    Matrix Infrared Spectroscopic and Theoretical Studies on the Reactions of Late Lanthanoid Atoms with Nitrous Oxide in Excess Argon

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    Reactions of laser-ablated late lanthanoid atoms (Gd, Tb, Dy, Ho, Er, Tm, Yb, and Lu) with N2O molecules in excess argon have been investigated using matrix-isolation infrared spectroscopy. Lanthanoid monoxide−dinitrogen complexes, OLn(N2) and OLnNN, are observed for Gd, Tb, Ho, and Er, and the OLnNN+ cations are observed for Gd to Lu except for Yb. The new products are characterized on the basis of isotopic shifts, mixed isotopic splitting patterns, and CCl4-doping experiments. Density functional theory calculations have been performed on the new species, which support identification of the OLn(N2), OLnNN, and OLnNN+ complexes from the matrix infrared spectra. Together with our earlier work involving early lanthanoid atoms, several trends are identified for the reactions of lanthanoid atoms with N2O molecules

    Complete Conversion of Hydrous Hydrazine to Hydrogen at Room Temperature for Chemical Hydrogen Storage

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    Complete Conversion of Hydrous Hydrazine to Hydrogen at Room Temperature for Chemical Hydrogen Storag

    Structural Investigation of Flexible 1,4-Bis(1,2,4-triazol-1-ylmethyl)benzene Ligand in Keggin-Based Polyoxometalate Frameworks

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    By introducing the flexible 1,4-bis(1,2,4-triazol-1-ylmethyl)benzene (btx) ligand into the molybdate system under the hydrothermal conditions, seven novel Keggin-based frameworks were obtained: [Ag(btx)]4[SiMo12O40]·2H2O (1), [Cu(btx)]4[SiMo12O40] (2), [Cu(btx)2]2[SiMo12O40] (3), [Zn(btx)2]2[SiMo12O40]·0.5H2O (4) and [M2(H2O)4(btx)3][SiMo12O40]·4H2O (M = Mn, Ni and Co) (5−7). Compound 1 contains 0D (zero dimensional) Keggin-based fragment, 1D polymer chain and 0D+1D poly-pseudo-rotaxane motif. Compound 2 exhibits interesting 1D+2D poly-pseudo-rotaxane architecture. Compound 3 has a 3D 4-connected diamond-related polymeric framework, which entraps the Keggin polyoxoanions into the stellate channels. Compound 4 contains isolated Keggin polyoxoanions and zipperlike polymer fragments, which are constructed from pairs of crumpled nets. Isostructural compounds 5−7 exhibit 2D→2D interpenetrated network structure featuring both polyrotaxane and polycatenane characters

    Catalysis with Metal Nanoparticles Immobilized within the Pores of Metal–Organic Frameworks

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    Metal–organic frameworks (MOFs) are highly ordered crystalline porous materials prepared by the self-assembly of metal ions and organic linkers having low-density framework structures of diversified topologies with tunable pore sizes and exceptionally large surface areas. Other than outstanding gas/molecule storage properties, loading of metal nanoparticles (MNPs) into the pores of MOFs could afford heterogeneous catalysts having advantages of controlling the particle growth to a nanosize region, resulting in highly active sites and enhanced catalytic performances, and these entrapped MNPs within MOF pores could be accessed by reactants for chemical transformations. This is a rapidly developing research area, and this Perspective addresses current achievements and future challenges for diverse MOF-immobilized MNPs within their pores, focusing especially on their preparation, characterization, and application as heterogeneous catalysts

    Structural Investigation of Flexible 1,4-Bis(1,2,4-triazol-1-ylmethyl)benzene Ligand in Keggin-Based Polyoxometalate Frameworks

    No full text
    By introducing the flexible 1,4-bis(1,2,4-triazol-1-ylmethyl)benzene (btx) ligand into the molybdate system under the hydrothermal conditions, seven novel Keggin-based frameworks were obtained: [Ag(btx)]4[SiMo12O40]·2H2O (1), [Cu(btx)]4[SiMo12O40] (2), [Cu(btx)2]2[SiMo12O40] (3), [Zn(btx)2]2[SiMo12O40]·0.5H2O (4) and [M2(H2O)4(btx)3][SiMo12O40]·4H2O (M = Mn, Ni and Co) (5−7). Compound 1 contains 0D (zero dimensional) Keggin-based fragment, 1D polymer chain and 0D+1D poly-pseudo-rotaxane motif. Compound 2 exhibits interesting 1D+2D poly-pseudo-rotaxane architecture. Compound 3 has a 3D 4-connected diamond-related polymeric framework, which entraps the Keggin polyoxoanions into the stellate channels. Compound 4 contains isolated Keggin polyoxoanions and zipperlike polymer fragments, which are constructed from pairs of crumpled nets. Isostructural compounds 5−7 exhibit 2D→2D interpenetrated network structure featuring both polyrotaxane and polycatenane characters
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