Two-Dimensional Cobalt(II) Benzoquinone Frameworks for Putative Kitaev Quantum Spin Liquid Candidates.

The realization and discovery of quantum spin liquid (QSL) candidate materials are crucial for exploring exotic quantum phenomena and applications associated with QSLs. Most existing metal-organic two-dimensional (2D) quantum spin liquid candidates have structures with spins arranged on the triangular or kagome lattices, whereas honeycomb-structured metal-organic compounds with QSL characteristics are rare. Here, we report the use of 2,5-dihydroxy-1,4-benzoquinone (X2dhbq, X = Cl, Br, H) as the linkers to construct cobalt(II) honeycomb lattices (NEt4)2[Co2(X2dhbq)3] as promising Kitaev-type QSL candidate materials. The high-spin d7 Co2+ has pseudospin-1/2 ground-state doublets, and benzoquinone-based linkers not only provide two separate superexchange pathways that create bond-dependent frustrated interactions but also allow for chemical tunability to mediate magnetic coupling. Our magnetization data show antiferromagnetic interactions between neighboring metal centers with Weiss constants from -5.1 to -8.5 K depending on the X functional group in X2dhbq linkers (X = Cl, Br, H). No magnetic transition or spin freezing could be observed down to 2 K. Low-temperature susceptibility (down to 0.3 K) and specific heat (down to 0.055 K) of (NEt4)2[Co2(H2dhbq)3] were further analyzed. Heat capacity measurements confirmed no long-range order down to 0.055 K, evidenced by the broad peak instead of the λ-like anomaly. Our results indicate that these 2D cobalt benzoquinone frameworks are promising Kitaev QSL candidates with chemical tunability through ligands that can vary the magnetic coupling and frustration.

Dual-Salts Localized High-Concentration Electrolyte for Li- and Mn-Rich High-Voltage Cathodes in Lithium Metal Batteries.

Limited electrochemical stability windows of conventional carbonate-based electrolytes pose a challenge to support the Lithium (Li)- and manganese (Mn)-rich (LMR) high-voltage cathodes in rechargeable Li-metal batteries (LMBs). To address this issue, a novel localized high-concentration electrolyte (LHCE) composition incorporating LiPF6 and LiTFSI as dual-salts (D-LHCE), tailored for high-voltage (>4.6 Vvs.Li) operation of LMR cathodes in LMBs is introduced. 7Li nuclear magnetic resonance and Raman spectroscopy revealed the characteristics of the solvation structure of D-LHCE. The addition of LiPF6 provides stable Al-current-collector passivation while the addition of LiTFSI improves the stability of D-LHCE by producing a more robust cathode-electrolyte interphase (CEI) on LMR cathode and solid-electrolyte interphase (SEI) on Li-metal anode. As a result, LMR/Li cell, using the D-LHCE, achieved 72.5% capacity retention after 300 cycles, a significant improvement compared to the conventional electrolyte (21.9% after 100 cycles). The stabilities of LMR CEI and Li-metal SEI are systematically analyzed through combined applications of electrochemical impedance spectroscopy and distribution of relaxation times techniques. The results present that D-LHCE concept represents an effective strategy for designing next-generation electrolytes for high-energy and high-voltage LMB cells.

Ionic Nitrogen-Doped Carbon Dots as Nonpolar Lubricant Additives at Low Effective Addition.

The poor compatibility with nonpolar lubricant still hinders the application of carbon dots (CDs) in lubrication. In addition, research proves that the existence of ionic structure and active groups on CDs are conducive to their lubricity. In order to obtain the ionic structures and good oil compatibility synchronously, a kind of ionic nitrogen-doped CDs (NCDs) was synthesized via the alkylation of nitrogen in NCDs and anion exchange. The new material could exhibit good tribological performance as poly alpha olefins (PAO4) additives with low addition. Moreover, an ionic liquid, [N44HH][DEHP], with the same anion was chosen as a comparison to investigate the role of NCD cations. The surface analyses demonstrate that NCD cations and phosphate ester anions adsorb on the friction interface to play a synergistic lubrication role during the friction process, which could generate a superior carbon-based tribofilm.

Norcantharidin promotes cancer radiosensitization through Cullin1 neddylation-mediated CDC6 protein degradation.

Radiotherapy (RT) is a conventional cancer therapeutic modality. However, cancer cells tend to develop radioresistance after a period of treatment. Diagnostic markers and therapeutic targets for radiosensitivity are severely lacking. Our recently published studies demonstrated that the cell division cycle (CDC6) is a critical molecule contributing to radioresistance, and maybe a potential therapeutic target to overcome radioresistance. In the present study, we for the first time reported that Norcantharidin (NCTD), a demethylated form of cantharidin, re-sensitized radioresistant cancer cells to overcome radioresistance, and synergistically promoted irradiation (IR)-induced cell killing and apoptosis by inducing CDC6 protein degradation. Mechanistically, NCTD induced CDC6 protein degradation through the ubiquitin-proteasome pathways. By using small interfering RNA (siRNA) interference or small compound inhibitors, we further determined that NCTD induced CDC6 protein degradation through a neddylation-dependent pathway, but not through Huwe1, Cyclin F, and APC/C-mediated ubiquitin-proteasome pathways. We screened the six most relevant Cullin subunits (CUL1, 2, 3, 4A, 4B, and 5) using siRNAs. The knockdown of Cullin1 but not the other five cullins remarkably elevated CDC6 protein levels. NCTD promoted the binding of Cullin1 to CDC6, thereby promoting CDC6 protein degradation through a Cullin1 neddylation-mediated ubiquitin-proteasome pathway. NCTD can be used in combination with radiotherapy to achieve better anticancer efficacy, or work as a radiosensitizer to overcome cancer radioresistance.

K3 SbS4 as a Potassium Superionic Conductor with Low Activation Energy for K-S Batteries.

Solid-state K-ion conducting electrolytes are key elements to address the current problems in K secondary batteries. Here, we report a sulfide-based K-ion conductor K3 SbS4 with a low-activation energy of 0.27 eV. W-doped K3-x Sb1-x Wx S4 (x=0.04, 0.06, 0.08, 0.10 and 0.12) compounds were also explored for increasing vacancy concentrations and improving ionic conductivity. Among them, K2.92 Sb0.92 W0.08 S4 exhibits the highest conductivity of 1.4×10-4  S cm-1 at 40 °C, which is among the best reported potassium-ion conductors at ambient temperature. In addition, K2.92 Sb0.92 W0.08 S4 is electrochemically stable with long-chained potassium polysulfide of K2 Sx . A room-temperature solid potassium-sulfur (K-S) battery system has therefore been successfully demonstrated, which is the first K-S battery prototype using non-commercial inorganic-based electrolyte to block the polysulfide shuttle.

Phase Transfer-Mediated Degradation of Ether-Based Localized High-Concentration Electrolytes in Alkali Metal Batteries.

Localized high-concentration electrolytes (LHCEs) have attracted interest in alkali metal batteries due to the advantages of forming stable solid-electrolyte interphases (SEIs) on anodes and good chemical/electrochemical stability. Herein, a new degradation mechanism is revealed for ether-based LHCEs that questions their compatibility with alkali metal anodes (Li, Na, and K). Specifically, the ether solvent reacts with alkali metals to generate solvated electrons (es - ) that attack hydrofluoroether co-solvents to form a series of byproducts. The ether solvent essentially acts as a phase-transfer reagent that continuously transfers electrons from solid-phase metals into the solution phase, thus inhibiting the formation of stable SEI and leading to continuous alkali metal corrosion. Switching to an ester-based solvating solvent or intercalation anodes such as graphite or molybdenum disulfide has been shown to avoid such a degradation mechanism due to the absence of es - .

Facile One-Step Metal-Organic Framework Surface Polymerization Method.

A simple one-step approach that only uses commercially available small-molecule reagents was developed for the construction of metal-organic framework (MOF)@polymer core-shell composite particles. Here, the MOF particles were incorporated into a typical reversible addition-fragmentation chain-transfer (RAFT) polymerization solution containing a solvent, a chain-transfer agent, an initiator, and a monomer mixture with at least one hydrogen-bond-donating monomer such as 2-hydroxyethyl methacrylate or acrylic acid. The elongation of polymer chains during polymerization gradually increases MOF/polymer interfacial interaction and eventually results in the adsorption of a random copolymer onto the MOF surface through hydrogen-bond cross-linking and MOF/polymer interfacial interaction. The continuous growth of the polymer leads to a uniform polymer coating on the MOF. Benefiting from the tacky polymer surface, these well-defined MOF@polymer composite particles can be further assembled into highly ordered monolayer composite thin films either alone or with an additional polymer matrix through the Langmuir-Blodgett technique.

Coating the Right Polymer: Achieving Ideal Metal-Organic Framework Particle Dispersibility in Polymer Matrixes Using a Coordinative Crosslinking Surface Modification Method.

This work describes the first generalizable method to modify various metal-organic framework (MOF) surfaces with polyimide, polysulfone, polycarbonate, and polymer of intrinsic microporosity-1 (PIM-1). The method first utilizes electrostatic adsorption to rapidly decorate positively charged MOF surfaces with a layer of negatively charged metal-organic nanocapsule, PgC5 Cu. After mixing with the polymer, the copper open metal sites on PgC5 Cu can coordinatively crosslink the polar functional groups on the surface polymer upon thermal activation thereby resulting in the immobilization of a uniform sub-10 nm polymer coating. We quantitatively analyzed the distribution of free path spacing between MOF particles and demonstrated that when the surface polymer matches the matrix polymer, the MOF dispersion was not only visually improved but also found to align perfectly with a theoretically predicted ideal dispersion model where no aggregation driving force was present.

Enhancing the Gas Separation Selectivity of Mixed-Matrix Membranes Using a Dual-Interfacial Engineering Approach.

We report a dual-interfacial engineering approach that uses a sub-20 nm polycrystalline MOF-74 shell as a transition phase to engineer the MOF-polymer interface. The application of a shell MOF layer divides the original single interface problem into two interfaces: MOF-MOF and MOF-polymer, which can be individually addressed. The greater external surface area created by the uneven MOF-74 shell containing high-density open metal sites allows the MOF to interact with 300% polymer at the interface compared to traditional MOF, thereby ensuring good interfacial compatibility. When applied on UiO-66-NH2, its respective mixed-matrix membranes exhibit a simultaneous increase of CO2/CH4 separation selectivity and CO2 permeability with increasing MOF loading, implying a defect-free interface. When applied on MOF-801, the mixed-matrix membranes exhibit an ethylene/ethane separation selectivity up to 5.91, a drastic 76% increase compared to that of the neat polymer owing to a "gas focusing" mechanism promoted by the preferred pore orientation in the MOF-74 layer. This represents one of the most selective ethylene/ethane separation membranes reported to date.

From K-O2 to K-Air Batteries: Realizing Superoxide Batteries on the Basis of Dry Ambient Air.

Although using an air cathode is the goal for superoxide-based potassium-oxygen (K-O2 ) batteries, prior studies were limited to pure oxygen. Now, the first K-air (dry) battery based on reversible superoxide electrochemistry is presented. Spectroscopic and gas chromatography analyses are applied to evaluate the reactivity of KO2 in ambient air. Although KO2 reacts with water vapor and CO2 to form KHCO3 , it is highly stable in dry air. With this knowledge, rechargeable K-air (dry) batteries were successfully demonstrated by employing dry air cathode. The reduced partial pressure of oxygen plays a critical role in boosting battery lifespan. With a more stable environment for the K anode, a K-air (dry) battery delivers over 100 cycles (>500 h) with low round-trip overpotentials and high coulombic efficiencies as opposed to traditional K-O2 battery that fails early. This work sheds light on the benefits and restrictions of employing the air cathode in superoxide-based batteries.

Enhanced circularly polarized luminescence dissymmetry of [Ru(bpy)3]2+ complexes in a 3D chiral framework: a study of transparent thin films.

Circularly polarized luminescence (CPL) plays an important role in the development of advanced optical devices. However, the design of CPL-active materials with a decent dissymmetry factor is still challenging. Here, we report CPL-active transparent thin films made from optically active ruthenium complexes [Ru(bpy)3]2+ embedded in chiral inorganic frameworks. Due to the unique chiral-in-chiral combination, the obtained [Ru(bpy)3][Zn2(C2O4)3] displays CPL activity with a dissymmetry factor of 5 × 10-3. The CPL measurements show that the luminescence dissymmetry factor can be effectively enhanced by one order of magnitude when an optically active [Ru(bpy)3]2+ complex is incorporated into a chiral inorganic framework compared to its solution form. This study not only emphasizes the potential of constructing CPL-active thin films with coordination polymers but also points out the importance of introducing extra chiral environment to improve the CPL effect.

Design and Synthesis of Cubic K3-2 x Bax SbSe4 Solid Electrolytes for K-O2 Batteries.

Developing K-ion conducting solid-state electrolytes (SSEs) plays a critical role in the safe implementation of potassium batteries. In this work, a chalcogenide-based potassium ion SSE is reported, K3 SbSe4 , which adopts a trigonal structure at room temperature. Single-crystal structural analysis reveals a trigonal-to-cubic phase transition at the low temperature of 50 °C, which is the lowest among similar compounds and thus provides easy access to the cubic phase. The substitution of barium for potassium in K3 SbSe4 leads to the creation of potassium vacancies, expansion of lattice parameters, and a transformation from a trigonal phase to a cubic phase. As a result, the maximum conductivity of K3-2 x Bax SbSe4 reaches around 0.1 mS cm-1 at 40 °C for K2.2 Ba0.4 SbSe4 , which is over two orders of magnitude higher than that of undoped K3 SbSe4 . This novel SSE is successfully employed in a K-O2 battery operating at room temperature where a polymer-laminated K2.2 Ba0.4 SbSe4 pellet serves as a separator between the oxygen cathode and the potassium metal anode. Effective protection of the K metal anode against corrosion caused by O2 is demonstrated.

PLK1 maintains DNA methylation and cell viability by regulating phosphorylation-dependent UHRF1 protein stability.

PLK1 is a key serine/threonine kinase as well as a master mitotic regulator, but it has never been reported that PLK1 regulates DNA methylation. In the present study, we for the first time found that PLK1 inhibition disrupted global DNA methylation and elevated the expression level of tumor suppressor genes. Mechanistically, we found that PLK1 interacts UHRF1 protein to induce its phosphorylation at serine 265. Phosphorylation is required for the maintenance of UHRF1 protein stability by recruiting a deubiquitinase USP7. Conversely, PLK1 inhibition decreases UHRF1 protein interaction with USP7 and activates the ubiquitin-proteasome pathway, thereby accelerating UHRF1 protein degradation. UHRF1 degradation decreases the recruitment of DNMT1 to chromatin, and decreases the level of genome-wide DNA methylation, thereby elevating the expression of tumor suppressor genes and decreasing cell viability. We here presented the first report on the novel role of PLK1 in DNA methylation maintenance through UHRF1-DNMT1 pathway, and revealed a novel anticancer mechanism of PLK1 inhibitors.

AR antagonists develop drug resistance through TOMM20 autophagic degradation-promoted transformation to neuroendocrine prostate cancer.

BACKGROUND: Prostate cancer(PCa) is the most commonly occurring male cancer in the USA. Abiraterone or Enzalutamide have been approved for the treatment of metastatic castration-resistant prostate cancer (CRPC). However, the treatment-emergent neuroendocrine PCa (t-NEPC) may develop, resulting in drug resistance in about 10-17% CRPC patients. The detailed mechanisms remain unclear.. METHODS: The expression correlation of TOMM20 and AR in PCa was determined by analyzing publicly available datasets, or by IHC staining in tumor specimens. The protein interaction of TOMM20 and AR was validated by co-immunoprecipitation or GST pull-down assay. The impact of TOMM20 depletion on drug sensitivity were elucidated by assays of cell proliferation, invasion, sphere formation, xenograft growth and intravenous metastasis. The intracellular ROS level was measured by flow cytometry, and the NEPC transdifferentiation and characteristics of cancer stem-like cells were validated by RNA-seq, RT-PCR and western blotting. RESULTS: The protein level of TOMM20 is positively correlated with AR in PCa cells and specimens. TOMM20 protein physically interacts with AR. AR antagonists induced the protein degradation of TOMM20 through autophagy-lysosomal pathway, thereby elevating the intracellular ROS level and activating PI3K/AKT signaling pathway. When TOMM20 was depleted, PCa cells underwent EMT, acquired the characteristics of cancer stem-like cells, and developed resistance to AR antagonists. The stable depletion of TOMM20 promoted the transdifferentiation of PCa adenocarcinoma into NEPC and metastasis. Conversely, the rescue of TOMM20 re-sensitized the resistant PCa cells to AR antagonists. CONCLUSIONS: TOMM20 protein degradation induced by AR antagonists promoted the transdifferentiation of PCa to NEPC, thereby revealing a novel molecular mechanism by which AR antagonists develop drug resistance through mitochondrial outer membrane-mediated signaling pathway. These findings suggested that the decreasing or loss of TOMM20 expression in PCa tissues might become a useful predictor of PCa resistance to AR antagonists.

The superior lubricating performance and unique mechanism of oil-soluble protic ionic liquids with short alkyl chains.

HYPOTHESIS: Ionic liquids (ILs), as lubricant additives, can greatly improve the lubricating behavior of the frictional interfaces. However, it is urgent to explore ILs with good oil solubility in nonpolar oils, and it is necessary to further study and verify the lubrication mechanism of ILs from the perspective of alkyl chain length. EXPERIMENTS: Five protic ILs (PILs) with varying alkyl chain lengths were synthesized by proton transfer method. As additives in PAO oil, their tribological properties were investigated on SRV-V tester. Through molecular dynamics simulation, the adsorption behavior of PILs at the frictional interface was illustrated. FINDINGS: The tribological properties of base oil could be significantly improved by adding PIL additives, but interestingly, PILs with short-chain anions showed better lubricating performance, which contradicted most of the early findings. Further analyses revealed that PILs achieved effective lubrication by the tribochemical interaction between anions and frictional interface, and the formation of cationic protective layer. However, PILs with shorter-chain anions form a denser protective layer that can better support the interfacial anions to participate in tribochemical reactions and thus abnormally exhibit superior lubricating performance than those with longer-chain anions.

Reverse synthesis of yolk-shell metal-organic frameworks.

We report the first examples of yolk-shell metal-organic framework (MOF) heterostructures based on topologically distinct MOFs: ZIF-8/ZIF-67 and UiO-66. This was accomplished through an innovative reverse synthesis strategy: A hollow UiO-66 was first constructed; the precusors of the ZIFs were then loaded into the cavity of hollow UiO-66 through a mixed solvent impregnation method; subsequent crystallization under solvothermal condition led to the formation of yolk-shell MOFs containing one or multiple ZIF particles confined within a chemically robust single crystalline UiO-66 shell.

UHRF1 promotes androgen receptor-regulated CDC6 transcription and anti-androgen receptor drug resistance in prostate cancer through KDM4C-Mediated chromatin modifications.

The UHRF1 and CDC6, oncogenes play critical roles in therapeutic resistance. In the present study, we found that UHRF1 mediates androgen receptor (AR)-regulated CDC6 transcription in prostate cancer cells. In prostate cancer tissues and cell lines, levels of UHRF1 and CDC6 were simultaneously upregulated, and this was associated with worse survival. UHRF1 silencing significantly promoted the cytotoxicity and anti-prostate cancer efficacy of bicalutamide in mouse xenografts by inhibiting CDC6 gene expression. UHRF1 promoted AR-regulated CDC6 transcription by binding to the CCAAT motif near the androgen response element (ARE) in the CDC6 promoter. We further found that UHRF1 promoted androgen-dependent chromatin occupancy of AR protein by recruiting the H3K9me2/3-specific demethyltransferase KDM4C and modifying the intense heterochromatin status. Altogether, we found for the first time that UHRF1 promotes AR-regulated CDC6 transcription through a novel chromatin modification mechanism and contributes to anti-AR drug resistance in prostate cancer. Targeting AR and UHRF1 simultaneously may be a novel and promising therapeutic modality for prostate cancer.

Nitrone [2]rotaxanes: simultaneous chemical protection and electrochemical activation of a functional group.

We report on the use of the hydrogen-bond-accepting properties of neutral nitrone moieties to prepare benzylic amide macrocycle-containing [2]rotaxanes in yields as high as 70%. X-ray crystallography showed the presence of up to four intercomponent hydrogen bonds between the amide groups of the macrocycle and the two nitrone groups of the thread. Dynamic (1)H NMR studies of the rates of macrocycle pirouetting in nonpolar solutions indicated that the amide-nitrone hydrogen bonds are particularly strong (approximately 1.3 and approximately 0.2 kcal mol(-1) stronger than similar amide-ester and amide-amide interactions, respectively). In addition to polarizing the N-O bond through hydrogen bonding, the rotaxane structure affects the chemistry of the nitrone groups in two significant ways: first, the intercomponent hydrogen bonding activates the nitrone groups to electrochemical reduction, a one-electron-reduction of the rotaxane being stabilized by a remarkable 400 mV (8.1 kcal mol(-1)) with respect to the same process in the thread; second, however, encapsulation protects the same functional groups from chemical reduction with an external reagent (and slows electron transfer to and from the electroactive groups in cyclic voltammetry experiments). Mechanical interlocking with a hydrogen-bonding molecular sheath thus provides a route to an encapsulated polarized functional group and radical anions of significant kinetic and thermodynamic stability.

Ambient Pressure X-ray Photoelectron Spectroscopy Investigation of Thermally Stable Halide Perovskite Solar Cells via Post-Treatment.

Long-term thermal stability is one limiting factor that impedes the commercialization of the perovskite solar cell. Inspired by our prior results from machine learning, we discover that coating a thin layer of 4,4'-dibromotriphenylamine (DBTPA) on top of a CH3NH3PbI3 layer can improve the stability of resultant solar cells. The passivated devices kept 96% of the original power conversion efficiency for 1000 h at 85 °C in a N2 atmosphere without encapsulation. Near-ambient pressure X-ray photoelectron spectroscopy (XPS) was employed to investigate the evolution of the composition and evaluate thermal and moisture stability by in situ studies. A comparison between pristine MAPbI3 films and DBTPA-treated films shows that the DBTPA treatment suppresses the escape of iodide and methylamine up to 150 °C under 5 mbar humidity. Furthermore, we have used attenuated total reflection Fourier transform infrared and XPS to probe the interactions between DBTPA and MAPbI3 surfaces. The results prove that DBTPA coordinates with the perovskite by Lewis acid-base and cation-π interaction. Compared with the 19.9% efficiency of the pristine sample, the champion efficiency of the passivated sample reaches 20.6%. Our results reveal DBTPA as a new post-treating molecule that leads not only to the improvement of the photovoltaic efficiency but also thermal and moisture stability.

Tracking and Visualization of Functional Domains in Stratified Metal-Organic Frameworks Using Gold Nanoparticles.

We report here a new technique for the identification and visualization of functional domains in stratified metal-organic frameworks (MOFs). The technique, namely, gold diffusion enabled domain identification, utilizes the diffusion of Au nanoparticles within MOF cavities to track and selectively stain the more Au-philic domain in an MOF particle thereby allowing direct observation of domains, determination of domain sequences, and, in certain cases, domain boundaries under transmission electron microscopy. This method is an excellent tool for studying MOF materials with complex domain hierarchy.