A Family of Binuclear Dysprosium(III) Radical Compounds with Magnetic Relaxation in ON and OFF States

Four binuclear dysprosium compounds incorporating the radical ligand 2-(4-oxidopyridyl)-4,4,5,5-tetramethylimidazolin-1-oxyl-3-oxide (PyNONIT) have been successfully synthesized under appropriate conditions. Centrosymmetric bimetallic Dy₂O₂ cores in all of the compounds through double-μ₂-oxygen atoms of the <i>N</i>-oxide groups are realized in a metal–radical approach for the first time. Dimers <b>1</b> and <b>2</b>, of the same formula {[Dy­(hfac)₃(PyNONIT)]₂}₂ (hfac = hexafluoroacetylacetonate) but obtained by different methods, which contain almost identical local symmetry of <i>D</i>_4<i>d</i> and Dy–(O)₂–Dy bridging fashion, however, display no out-of-phase alternating-current (ac) signal for <b>1</b> and slow relaxation of the magnetization for <b>2</b> corresponding to the difference of the crystal packing mode. The adduct ([Dy­(hfac)₃(PyNONIT)]₂[Dy_0.5(hfac)_1.5(H₂O)]₂) (<b>3</b>) consists of two items, the dimer [Dy­(hfac)₃(PyNONIT)]₂ and the monomer [Dy­(hfac)₃(H₂O)₂], where the symmetry of Dy^III ion in Dy₂O₂ decreases to <i>D</i>_2<i>d</i>, showing slow relaxation of the magnetization at lower temperature. Interestingly, a moisture-mediated reversible solid transformation between <b>1</b> and ([Dy­(hfac)₃(H₂O)­(PyNONIT)]₂) (<b>4</b>) has been investigated. Spongelike <b>1</b> can undergo a transition from eight to nine coordination at room temperature through hydration. A different coordination field is mostly responsible for no ac signal noticed for <b>4</b>. The structural diversity of the Dy₂ family provides an opportunity to expand the investigation on 4f single-molecule magnets. Approaches that the relaxation of the supramolecular dimer can be tuned to ON and OFF states modulated by the packing mode and ligand field are presented

Polymeric Perturbation to the Magnetic Relaxations of the <i>C</i>_2<i>v</i>-Symmetric [Er(Cp)₂(OBu)₂]⁻ Anion

To test the coordination symmetry effect on the magnetization-reversal barrier trend of Er^III-based single-ion magnets, the <i>C</i>_2<i>v</i>-symmetric organolanthanide anion [Er­(Cp)₂(O^<i>t</i>Bu)₂]⁻ has been incorporated with different countercations, resulting in two structures, namely, the discrete [K₂(Cp)­(18-C-6)₂]­[Er­(Cp)₂(O^<i>t</i>Bu)₂] (<b>1</b>) and the polymeric [ErK₂(Cp)₃(O^<i>t</i>Bu)₂(THF)₂]_n (<b>2</b>), where 18-C-6 = 18-crown-6 ether and Cp = cyclopentadienide. Surprisingly, the polymeric <b>2</b> exhibits much stronger field-induced magnetization relaxing behavior compared to the monomeric <b>1</b>. Such disparate dynamic magnetism is attributable to the subtle coordination environmental perturbations of the central Er^III ions

Redox-Active Cobalt(II/III) Metal–Organic Framework for Selective Oxidation of Cyclohexene

We report herein a new cobalt­(II/III) mixed-valence metal–organic framework formulated as [Co^IICo₂^III(μ₃-O)­(bdc)₃(tpt)]·guest <b>1</b>, where bdc = benzene-1,4-dicarboxylate and tpt = 2,4,6-tri­(4-pyridinyl)-1,3,5-triazine, which can be used as a redox-active heterogeneous catalyst for selective oxidation of cyclohexene on the allylic position without destroying the adjacent double bond. Two oxidants were chosen to demonstrate this result. For using <i>tert</i>-butyl hydroperoxide, the conversion rate is 63% and only allylic oxidation products (<i>tert</i>-butyl-2-cyclohexenyl-1-peroxide, 86%; 2-cyclohexen-1-one, 14%) are found, whereas if using O₂ as oxidant, a total conversion of 38% is achieved and also only the allylic oxidation products (cyclohexenyl hydroperoxide, 72%; 2-cyclohexen-1-one, 20%; and cyclohex-2-en-1-ol, 8%) are found. The absence of any adduct on the double bond may be due to the unique radical chain mechanism triggered by the mixed-valent [Co^IICo₂^III(μ₃-O)] centers

A Family of Binuclear Dysprosium(III) Radical Compounds with Magnetic Relaxation in ON and OFF States

Four binuclear dysprosium compounds incorporating the radical ligand 2-(4-oxidopyridyl)-4,4,5,5-tetramethylimidazolin-1-oxyl-3-oxide (PyNONIT) have been successfully synthesized under appropriate conditions. Centrosymmetric bimetallic Dy₂O₂ cores in all of the compounds through double-μ₂-oxygen atoms of the <i>N</i>-oxide groups are realized in a metal–radical approach for the first time. Dimers <b>1</b> and <b>2</b>, of the same formula {[Dy­(hfac)₃(PyNONIT)]₂}₂ (hfac = hexafluoroacetylacetonate) but obtained by different methods, which contain almost identical local symmetry of <i>D</i>_4<i>d</i> and Dy–(O)₂–Dy bridging fashion, however, display no out-of-phase alternating-current (ac) signal for <b>1</b> and slow relaxation of the magnetization for <b>2</b> corresponding to the difference of the crystal packing mode. The adduct ([Dy­(hfac)₃(PyNONIT)]₂[Dy_0.5(hfac)_1.5(H₂O)]₂) (<b>3</b>) consists of two items, the dimer [Dy­(hfac)₃(PyNONIT)]₂ and the monomer [Dy­(hfac)₃(H₂O)₂], where the symmetry of Dy^III ion in Dy₂O₂ decreases to <i>D</i>_2<i>d</i>, showing slow relaxation of the magnetization at lower temperature. Interestingly, a moisture-mediated reversible solid transformation between <b>1</b> and ([Dy­(hfac)₃(H₂O)­(PyNONIT)]₂) (<b>4</b>) has been investigated. Spongelike <b>1</b> can undergo a transition from eight to nine coordination at room temperature through hydration. A different coordination field is mostly responsible for no ac signal noticed for <b>4</b>. The structural diversity of the Dy₂ family provides an opportunity to expand the investigation on 4f single-molecule magnets. Approaches that the relaxation of the supramolecular dimer can be tuned to ON and OFF states modulated by the packing mode and ligand field are presented

Polymeric Perturbation to the Magnetic Relaxations of the <i>C</i>_2<i>v</i>-Symmetric [Er(Cp)₂(OBu)₂]⁻ Anion

To test the coordination symmetry effect on the magnetization-reversal barrier trend of Er^III-based single-ion magnets, the <i>C</i>_2<i>v</i>-symmetric organolanthanide anion [Er­(Cp)₂(O^<i>t</i>Bu)₂]⁻ has been incorporated with different countercations, resulting in two structures, namely, the discrete [K₂(Cp)­(18-C-6)₂]­[Er­(Cp)₂(O^<i>t</i>Bu)₂] (<b>1</b>) and the polymeric [ErK₂(Cp)₃(O^<i>t</i>Bu)₂(THF)₂]_n (<b>2</b>), where 18-C-6 = 18-crown-6 ether and Cp = cyclopentadienide. Surprisingly, the polymeric <b>2</b> exhibits much stronger field-induced magnetization relaxing behavior compared to the monomeric <b>1</b>. Such disparate dynamic magnetism is attributable to the subtle coordination environmental perturbations of the central Er^III ions

Redox-Active Cobalt(II/III) Metal–Organic Framework for Selective Oxidation of Cyclohexene

We report herein a new cobalt­(II/III) mixed-valence metal–organic framework formulated as [Co^IICo₂^III(μ₃-O)­(bdc)₃(tpt)]·guest <b>1</b>, where bdc = benzene-1,4-dicarboxylate and tpt = 2,4,6-tri­(4-pyridinyl)-1,3,5-triazine, which can be used as a redox-active heterogeneous catalyst for selective oxidation of cyclohexene on the allylic position without destroying the adjacent double bond. Two oxidants were chosen to demonstrate this result. For using <i>tert</i>-butyl hydroperoxide, the conversion rate is 63% and only allylic oxidation products (<i>tert</i>-butyl-2-cyclohexenyl-1-peroxide, 86%; 2-cyclohexen-1-one, 14%) are found, whereas if using O₂ as oxidant, a total conversion of 38% is achieved and also only the allylic oxidation products (cyclohexenyl hydroperoxide, 72%; 2-cyclohexen-1-one, 20%; and cyclohex-2-en-1-ol, 8%) are found. The absence of any adduct on the double bond may be due to the unique radical chain mechanism triggered by the mixed-valent [Co^IICo₂^III(μ₃-O)] centers

Additional file 1 of LncRNA LBX2-AS1 promotes proliferation and migratory capacity of clear cell renal cell carcinoma through mitophagy

Additional file 1. Table S1. Sequences of primers used in qPCR

Filling the Missing Links of M_3<i>n</i> Prototype 3d-4f and 4f Cyclic Coordination Cages: Syntheses, Structures, and Magnetic Properties of the Ni₁₀Ln₅ and the Er_3<i>n</i> Wheels

In this paper, we proposed a number rule for 3d-4f and 4f cyclic coordination cages (CCCs); that is, CCCs consisting of vertex-sharing M₄(μ₃-OH)₄ (M = 3d transition metal or 4f lanthanide ions) units should have 3 × <i>n</i> metal centers (abbreviated M_3<i>n</i>), where <i>n</i> represents the number of the M₄(μ₃-OH)₄ subunits. Under this number rule we reasoned that some species of CCCs, for example, the pentadecanuclear 3d-4f wheel and the pure 4f wheels with 9 or 18 centers, should practically have existed. However, there are no such complexes reported in the literature. To realize such CCCs we employed a mixed-ligand approach, that is, to simultaneously use the primary and the ancillary ligands for syntheses. This approach successfully leads to the isolation of two families of CCCs, namely, the Ni₁₀Ln₅ (Ln = Gd and Y) mixed-metal wheels and the Er_3<i>n</i> (<i>n</i> = 4, 5, and 6) pure 4f metal wheels. These two families of CCCs unambiguously fill the missing links of the M_3<i>n</i> prototype CCCs. Moreover, dominated ferromagnetic interaction indicates high ground-spin state for the Gd₅Ni₁₀ wheel. The ferromagnetic interactions between the nickel centers are verified using the diamagnetic Y­(III) analogue, which reveals an averaged coupling constant (<i>J</i> = 2.7 cm^–1), while accompanied by a large negative zero-field splitting parameter (<i>D</i> = −6.1 cm^–1) for single Ni­(II) ions. Interestingly, the Y­(III)-diluted Er₁₂ wheel shows slow magnetic relaxation behavior, presumably indicating the magnetically anisotropic nature of the erbium­(III) ions

Structural Diversity of Four Metal–Organic Frameworks Based on Linear Homo/Heterotrinuclear Nodes with Furan-2,5-dicarboxylic Acid: Crystal Structures and Luminescent and Magnetic Properties

Four new homo- and heterometallic metal–organic frameworks (MOFs) based on linear homo/heterotrinuclear nodes, namely, {[NH₂(CH₃)₂]₂­[Co₃(FDA)₄­(CH₃OH)₂]}_<i>n</i> (<b>1</b>), {[NH₂(CH₃)₂]₂­[Co₃(FDA)₄]­·2DMF}_<i>n</i> (<b>2</b>), {[Gd₂Co­(FDA)₄(H₂O)₄]·2H₂O}_<i>n</i> (<b>3</b>), and {[Dy₂Co­(FDA)₄(glycol)₂]·2H₂O}_<i>n</i> (<b>4</b>) (H₂FDA = furan-2,5-dicarboxylic acid), were obtained under solvothermal conditions and characterized by single crystal X-ray diffraction, magnetic susceptibility, and luminescence measurements. The building blocks of four MOFs are linear trinuclear clusters stabilized by carboxylic groups, but the three-dimensional frameworks are different. MOFs <b>1</b> and <b>2</b> are both <b>pcu</b> nets with a point symbol of (4¹².6³), whereas MOFs <b>3</b> and <b>4</b> exhibit <b>3,10T9</b> and <b>tfz-d</b> nets with the point symbols of (4¹⁸.6²⁴.8³)­(4³)₂ and (4³)₂(4⁶.6¹⁸.8⁴), respectively. Magnetic susceptibility measurements indicate that there are antiferromagnetic interactions in <b>1</b>–<b>3</b>, while <b>4</b> displays interesting ferromagnetic interactions between Co­(II) and Dy­(III) ions. Luminescence investigation of <b>4</b> shows intense and characteristic emission bands of Dy­(III) ions in the solid state

Image_4_Comprehensive investigation into cuproptosis in the characterization of clinical features, molecular characteristics, and immune situations of clear cell renal cell carcinoma.tif

BackgroundCopper-induced cell death has been widely investigated in human diseases as a form of programmed cell death (PCD). The newly recognized mechanism underlying copper-induced cell death provided us creative insights into the copper-related toxicity in cells, and this form of PCD was termed cuproptosis.MethodsThrough consensus clustering analysis, ccRCC patients from TCGA database were classified into different subgroups with distinct cuproptosis-based molecular patterns. Analyses of clinical significance, long-term survival, and immune features were performed on subgroups accordingly. The cuproptosis-based risk signature and nomogram were constructed and validated relying on the ccRCC cohort as well. The cuproptosis scoring system was generated to better characterize ccRCC patients. Finally, in vitro validation was conducted using ccRCC clinical samples and cell lines.ResultPatients from different subgroups displayed diverse clinicopathological features, survival outcomes, tumor microenvironment (TME) characteristics, immune-related score, and therapeutic responses. The prognostic model and cuproptosis score were well validated and proved to efficiently distinguish the high risk/score and low risk/score patients, which revealed the great predictive value. The cuproptosis score also tended out to be intimately associated with the prognosis and immune features of ccRCC patients. Additionally, the hub cuproptosis-associated gene (CAG) FDX1 presented a dysregulated expression pattern in human ccRCC samples, and it was confirmed to effectively promote the killing effects of copper ionophore elesclomol as a direct target. In vitro functional assays revealed the prominent anti-cancer role of FDX1 in ccRCC.ConclusionCuproptosis played an indispensable role in the regulation of TME features, tumor progression, and long-term prognosis of ccRCC.</p