Dual Structure of a Vanadyl-Based Molecular Qubit Containing a Bis(ß-diketonato) Ligand.

We designed [VO(bdhb)] (1') as a new electronic qubit containing an oxovanadium(IV) ion (S = 1/2) embraced by a single bis(ß-diketonato) ligand [H2bdhb = 1,3-bis(3,5-dioxo-1-hexyl)benzene]. The synthesis afforded three different crystal phases, all of which unexpectedly contain dimers with formula [(VO)2(bdhb)2] (1). A trigonal form (1h) with a honeycomb structure and 46% of solvent-accessible voids quantitatively transforms over time into a monoclinic solvatomorph 1m and minor amounts of a triclinic solventless phase (1a). In a static magnetic field, 1h and 1m have detectably slow magnetic relaxation at low temperatures through quantum tunneling and Raman mechanisms. Angle-resolved electron paramagnetic resonance (EPR) spectra on single crystals revealed signatures of low-dimensional magnetic behavior, which is solvatomorph-dependent, being the closest interdimer V···V separations (6.7-7.5 Å) much shorter than intramolecular V···V distances (11.9-12.1 Å). According to 1H diffusion ordered spectroscopy (DOSY) and EPR experiments, the complex adopts the desired monomeric structure in organic solution and its geometry was inferred from density functional theory (DFT) calculations. Spin relaxation measurements in a frozen toluene-d8/CD2Cl2 matrix yielded Tm values reaching 13 µs at 10 K, and coherent spin manipulations were demonstrated by Rabi nutation experiments at 70 K. The neutral quasi-macrocyclic structure, featuring nuclear spin-free donors and additional possibilities for chemical functionalization, makes 1' a new convenient spin-coherent building block in quantum technologies.

A Heterometallic Porphyrin Dimer as a Potential Quantum Gate: Magneto-Structural Correlations and Spin Coherence Properties.

In the development of two-qubit quantum gates, precise control over the intramolecular spin-spin interaction between molecular spin units plays a pivotal role. A weak but measurable exchange coupling is especially important for achieving selective spin addressability that allows controlled manipulation of the computational basis states |00⟩ |01⟩ |10⟩ |11⟩ by microwave pulses. Here, we report the synthesis and Electron Paramagnetic Resonance (EPR) study of a heterometallic meso-meso (m-m) singly-linked VIV O-CuII porphyrin dimer. X-band continuous wave EPR measurements in frozen solutions suggest a ferromagnetic exchange coupling of ca. 8 ⋅ 10-3  cm-1 . This estimation is supported by Density Functional Theory calculations, which also allow disentangling the ferro- and antiferromagnetic contributions to the exchange. Pulsed EPR experiments show that the dimer maintains relaxation times similar to the monometallic CuII porphyrins. The addressability of the two individual spins is made possible by the different g-tensors of VIV and CuII -ions, in contrast to homometallic dimers where tilting of the porphyrin planes plays a key role. Therefore, single-spin addressability in the heterometallic dimer can be maintained even with small tilting angles, as expected when deposited on surface, unlocking the full potential of molecular quantum gates for practical applications.

Effects of ibandronate sodium, a nitrogen-containing bisphosphonate, on intermediate-conductance calcium-activated potassium channels in osteoclast precursor cells (RAW 264.7).

Ibanonate sodium (Iban), a nitrogen-containing bisphosphonate, is recognized to reduce skeletal complications through an inhibition of osteoclast-mediated bone resorption. However, how this drug interacts with ion channels in osteoclasts and creates anti-osteoclastic activity remains largely unclear. In this study, we investigated the possible effects of Iban and other related compounds on ionic currents in the osteoclast precursor RAW 264.7 cells. Iban suppressed the amplitude of whole-cell K(+) currents (I K) in a concentration-dependent manner with an IC50 value of 28.9 µM. The I K amplitude was sensitive to block by TRAM-34 and Iban-mediated inhibition of I K was reversed by further addition of DCEBIO, an activator of intermediate-conductance Ca(2+)-activated K(+) (IKCa) channels. Intracellular dialysis with Iban diminished I K amplitude and further addition of ionomycin reversed its inhibition. In 17ß-estradiol-treated cells, Iban-mediated inhibition of I K remained effective. In cell-attached current recordings, Iban applied to bath did not modify single-channel conductance of IKCa channels; however, it did reduce channel activity. Iban-induced inhibition of IKCa channels was voltage-dependent. As IKCa-channel activity was suppressed by KN-93, subsequent addition of Iban did not further decrease the channel open probability. Iban could not exert any effect on inwardly rectifying K(+) current in RAW 264.7 cells. Under current-clamp recordings, Iban depolarized the membrane of RAW 264.7 cells and DCEBIO reversed Iban-induced depolarization. Iban also suppressed lipopolysaccharide-stimulated migration of RAW 264.7 cells in a concentration-dependent manner. Therefore, the inhibition by Iban of IKCa channels would be an important mechanism underlying its actions on the functional activity of osteoclasts occurring in vivo.

Spin-Lattice Relaxation and Spin-Phonon Coupling of ns1 Metal Ions at the Surface.

To use transition metal ions for spin-based applications, it is essential to understand fundamental contributions to electron spin relaxation in different ligand environments. For example, to serve as building blocks for a device, transition metal ion-based molecular qubits must be organized on surfaces and preserve long electron spin relaxation times, up to room temperature. Here we propose monovalent group 12 ions (Zn+ and Cd+) as potential electronic metal qubits with an ns1 ground state. The relaxation properties of Zn+ and Cd+, stabilized at the interface of porous aluminosilicates, are investigated and benchmarked against vanadium (3d1) and copper (3d9) ions. The spin-phonon coupling has been evaluated through DFT modeling and found to be negligible for the ns1 states, explaining the long coherence time, up to 2 µs, at room temperature. These so far unexplored metal qubits may represent viable candidates for room temperature quantum operations and sensing.

Synergistic Effect of the Anode Interface of Garnet-Type All-Solid-State Batteries.

Next-generation lithium-ion batteries must have high energy density and safety, making the development of all-solid-state batteries imperative. One of the biggest advantages of an all-solid-state lithium-ion battery (ASSLIB) is that its alloy uses lithium metal as an anode while ignoring its flammability and other dangers. Herein, high-conductivity garnet-type Li6.75La3Zr1.75Ta0.25O12 (LLZTO) was chosen as the solid electrolyte part of an all-solid-state battery. A composite anode was formed by melting Li and MXene-MAX together, reducing the interface impedance from 566 to 55 Ω cm2. The Li-MXene|LLZTO|LFP full battery displayed a high initial discharge capacity of 163.0 mAh g-1 and a Coulombic efficiency of 97.0% and maintained 90.2% of its discharge capacity over 100 cycles, but it did not maintain a good overpotential. Therefore, the synergistic effect of Li-MXene-Pt will highly improve the performance of the full battery because of its high initial discharge capacity of 150.0 mAh g-1 and Coulombic efficiency of 95.5%, discharge capacity maintained at 93.3% over 100 cycles, and low overpotential of 0.04 V.

In Situ and Low-Cost Improvement of the Lithium Anode Interface in Garnet-Type Solid-State Electrolytes.

In recent years, the development of electric vehicles and environmental concerns have made necessary improvements in the energy density and safety of lithium-ion batteries. Therefore, the development of all-solid-state lithium-ion batteries (ASSLIBs) has become imperative. One advantage of ASSLIBs is their potential for downsizing with the use of lithium metal as the anode. However, in this study, a garnet-type solid electrolyte (Li6.75La3Zr1.75Ta0.25O12) was used, which has low reactivity with lithium metal. Thus, interface modification using CaCl2 was employed to form a Li-Ca-Cl composite anode. The interfacial resistance was remarkably reduced to 7 Ω cm2, and the symmetric cell exhibited stable cycling for 1200 h at room temperature and a current density of 0.1 mA cm-2. The voltage ranged from ±15 to ±16 mV. The full cell demonstrated a high initial discharge capacity of 149.2 mA h g-1 and a Coulombic efficiency of 98.0% while maintaining a discharge capacity retention of 91.3% after 100 cycles. These findings lay a solid foundation for future commercial applications as interface modification was achieved through a simple spin-coating process using low-cost CaCl2 (0.7 USD g-1).

Robust and Intimate Interface Enabled by Silicon Carbide as an Additive to Anodes for Lithium Metal Solid-State Batteries.

Garnet-type solid-state electrolytes are among the most reassuring candidates for the development of solid-state lithium metal batteries (SSLMB) because of their wide electrochemical stability window and chemical feasibility with lithium. However, issues such as poor physical contact with Li metal tend to limit their practical applications. These problems were addressed using ß-SiC as an additive to the Li anode, resulting in improved wettability over Li6.75 La3 Zr1.75 Ta0.25 O12 (LLZTO) and establishing an improved interfacial contact. At the Li-SiC|LLZTO interface, intimacy was induced by a lithiophilic Li4 SiO4 phase, whereas robustness was attained through the hard SiC phase. The optimized Li-SiC|LLZTO|Li-SiC symmetric cell displayed a low interfacial impedance of 10â€…Ω cm2 and superior cycling stability at varying current densities up to 5800 h. Moreover, the modified interface could achieve a high critical current density of 4.6 mA cm-2 at room temperature and cycling stability of 1000 h at 3.5 mA cm-2 . The use of mechanically superior materials such as SiC as additives for the preparation of a composite anode may serve as a new strategy for robust garnet-based SSLMB.

Short-Range Electronic Interactions between Vanadium and Molybdenum in Bimetallic SAPO-5 Catalysts Revealed by Hyperfine Spectroscopy.

Engineering two cooperative sites into a catalyst implies the onset of synergistic effects related to the existence of short-range electronic interactions between two metal components. However, these interactions and the relative structure-property correlations are often difficult to obtain. Here we show that hyperfine spectroscopy has the potential to reveal the presence of V4+-O-Mo6+ linkages assessing the degree of spin density transfer from paramagnetic V4+ species to proximal oxo-bridged Mo6+ metal ions. The dimer species were prepared by adsorption of Mo(CO)6 in the pores of SAPO-5, followed by thermal decomposition and oxidation and subsequent grafting of anhydrous VCl4(g) followed by hydrolysis and dehydration. The metal species react with SAPO protons during the exchange process and generate new Lewis acid sites, which act as redox centers. X- and Q-band EPR and HYSCORE experiments have been employed to monitor the local environment of V4+ species obtaining direct evidence for spin delocalization over 27Al, 31P, 95Mo, and 97Mo nuclei, demonstrating the presence of bimetallic V-O-Mo well-defined structures.

Spontaneous In Situ Formation of Lithium Metal Nitride in the Interface of Garnet-Type Solid-State Electrolyte by Tuning of Molten Lithium.

All-solid-state lithium-ion batteries (ASSLIBs) have attracted much attention owing to their high energy density and safety and are known as the most promising next-generation LIBs. The biggest advantage of ASSLIBs is that it can use lithium metal as the anode without any safety concerns. This study used a high-conductivity garnet-type solid electrolyte (Li6.75La3Zr1.75Ta0.25O12, LLZTO) and Li-Ga-N composite anode synthesized by mixing melted Li with GaN. The interfacial resistance was reduced from 589 to 21 Ω cm2, the symmetry cell was stably cycled for 1000 h at a current density of 0.1 mA cm-2 at room temperature, and the voltage range only changed from ±30 to ±40 mV. The full cell of Li-Ga-N|LLZTO|LFP exhibited a high first-cycle discharge capacity of 152.2 mAh g-1 and Coulombic efficiency of 96.5% and still maintained a discharge capacity retention of 91.2% after 100 cycles. This study also demonstrated that Li-Ga-N had been shown as two layers. Li3N shows more inclined to be closer to the LLZTO side. This method can help researchers understand what interface improvements can occur to enhance the performance of all-solid-state batteries in the future.

Quantum spin coherence and electron spin distribution channels in vanadyl-containing lantern complexes.

We herein investigate the heterobimetallic lantern complexes [PtVO(SOCR)4] as charge neutral electronic qubits based on vanadyl complexes (S = 1/2) with nuclear spin-free donor atoms. The derivatives with R = Me (1) and Ph (2) give highly resolved X-band EPR spectra in frozen CH2Cl2/toluene solution, which evidence the usual hyperfine coupling with the 51V nucleus (I = 7/2) and an additional superhyperfine interaction with the I = 1/2 nucleus of the 195Pt isotope (natural abundance ca. 34%). DFT calculations ascribe the spin density delocalization on the Pt2+ ion to a combination of π and δ pathways, with the former representing the predominant channel. Spin relaxation measurements in frozen CD2Cl2/toluene-d8 solution between 90 and 10 K yield Tm values (1-6 µs in 1 and 2-11 µs in 2) which compare favorably with those of known vanadyl-based qubits in similar matrices. Coherent spin manipulations indeed prove possible at 70 K, as shown by the observation of Rabi oscillations in nutation experiments. The results indicate that the heavy Group 10 metal ion is not detrimental to the coherence properties of the vanadyl moiety and that Pt-VO lanterns can be used as robust spin-coherent building blocks in materials science and quantum technologies.

Evidence for inhibitory effects of flupirtine, a centrally acting analgesic, on delayed rectifier k(+) currents in motor neuron-like cells.

Flupirtine (Flu), a triaminopyridine derivative, is a centrally acting, non-opiate analgesic agent. In this study, effects of Flu on K(+) currents were explored in two types of motor neuron-like cells. Cell exposure to Flu decreased the amplitude of delayed rectifier K(+) current (I(K(DR))) with a concomitant raise in current inactivation in NSC-34 neuronal cells. The dissociation constant for Flu-mediated increase of I(K(DR)) inactivation rate was about 9.8 µM. Neither linopirdine (10 µM), NMDA (30 µM), nor gabazine (10 µM) reversed Flu-induced changes in I(K(DR)) inactivation. Addition of Flu shifted the inactivation curve of I(K(DR)) to a hyperpolarized potential. Cumulative inactivation for I(K(DR)) was elevated in the presence of this compound. Flu increased the amplitude of M-type K(+) current (I(K(M))) and produced a leftward shift in the activation curve of I(K(M)). In another neuronal cells (NG108-15), Flu reduced I(K(DR)) amplitude and enhanced the inactivation rate of I(K(DR)). The results suggest that Flu acts as an open-channel blocker of delayed-rectifier K(+) channels in motor neurons. Flu-induced block of I(K(DR)) is unlinked to binding to NMDA or GABA receptors and the effects of this agent on K(+) channels are not limited to its action on M-type K(+) channels.

Chromium Environment within Cr-Doped Silico-Aluminophosphate Molecular Sieves from Spin Density Studies.

X-/Q-band electron paramagnetic resonance (EPR) and hyperfine sublevel correlation (HYSCORE) spectroscopies have been employed, in conjunction with density functional theory (DFT) modeling, to determine the location of Cr5+ions in SAPO-5 zeotype materials. The interaction of the unpaired electron of the paramagnetic Cr5+ species with 27Al could be resolved, allowing for the first detailed structural analysis of Cr5+ paramagnetic ions in SAPO materials. The interpretation of the experimental results is corroborated by DFT modeling, which affords a microscopic description of the system investigated. The EPR-active species is found to be consistent with isolated Cr5+ species isomorphously substituted in the framework at P5+ sites.

Extensively Reducing Interfacial Resistance by the Ultrathin Pt Layer between the Garnet-Type Solid-State Electrolyte and Li-Metal Anode.

All-solid-state Li-ion batteries (ASSLIBs), also known as next-generation batteries, have attracted much attention due to their high energy density and safety. The best advantage of ASSLIBs is the Li-metal anodes that could be used without safety issues. In this study, a highly conductive garnet solid electrolyte (Li6.75La3Zr1.75Ta0.25O12, LLZTO) was used in the ASSLIB, and a Pt film was used to modify the surface of LLZTO to prove the solution of the Li-metal anode for LLZTO. Li-Pt alloy was synthesized to improve the wettability and contact of the interface. The interfacial resistance was reduced by 21 times, at only 9 Ω cm2. The symmetric cell could stably cycle over 3500 h at a current density of 0.1 mA cm-2. The full cell of Li|Li-Pt|LLZTO|LiFePO4 and Li|Li-Pt|LLZTO|LiMn0.8Fe0.2PO4 achieved high stability in terms of battery performance. Point-to-point contact transformed into homogeneous surface contact made the Li-ion flux faster and more stable. This surface modification method could provide researchers with a new choice for fixing interface issues and promoting the application of high-performance ASSLIBs in the future.

Interface Between Solid-State Electrolytes and Li-Metal Anodes: Issues, Materials, and Processing Routes.

Li metal, which has a high theoretical capacity and negative electrochemical potential, is regarded as the "holy grail" in Li-ion batteries. However, the flammable nature of liquid electrolyte leads to safety issues. Hence, the cooperation of solid-state electrolyte and Li-metal anode is demanded. However, the short cycle life induced by interfacial issues is the main challenge faced by their cooperation. In this review, dendrite and interfacial side reactions are comprehensively analyzed as the main interfacial problems. Meanwhile, the "state-of-the-art" interphase materials are summarized. The challenges faced by each kind of material are underscored. Moreover, different processing routes to fabricate artificial interphase are also investigated from an engineering perspective. The processing routes suitable for mass production are also underscored.

Arecoline inhibits intermediate-conductance calcium-activated potassium channels in human glioblastoma cell lines.

Arecoline (ARE) is an alkaloid-type natural product from areca nut. This compound has numerous pharmacological and toxicological effects. Whether this agent interacts with ion channels to perturb functional activity of cells remains unknown. The effects of ARE on ionic currents were studied in glioma cell lines (U373 and U87MG) using patch-clamp technique. Like TRAM-34(1-[(2-chlorophenyl)-diphenylmethyl]pyrazole), ARE suppressed the amplitude of whole-cell voltage-gated K(+) currents in U373 cells elicited by a ramp voltage clamp. In cell-attached configuration, ARE did not modify the single-channel conductance of intermediate-conductance Ca(2+)-activated K(+) (IKCa) channels; however, it did reduce channel activity. Its inhibition of IKCa channels was accompanied by a significant lengthening in the slow component of mean closed time of IKCa channels. Based on minimal kinetic scheme, the dissociation constant (KD) required for ARE-mediated prolongation of mean closed time was 11.2µM. ARE-induced inhibition of IKCa channels was voltage-dependent. Inability of ARE to perturb the activity of large-conductance Ca(2+)-activated K(+) (BKCa) channels was seen. Under current-clamp recordings, ARE depolarized the membrane of U373 cells and DCEBIO reversed ARE-induced depolarization. Similarly, ARE suppressed IKCa-channel activities in oral keratinocytes. This study provides the evidence that ARE block IKCa channels in a concentration, voltage and state-dependent manner. ARE-induced block of IKCa channels is unrelated to the binding of muscarinic receptors. The effects of ARE on these channels may partially be responsible for the underlying cellular mechanisms by which it influences the functional activities of glioma cells or oral keratinocytes, if similar findings occur in vivo.

Non-invasive evaluation of therapeutic response in keloid scar using diffuse reflectance spectroscopy.

The pathogenesis and ideal treatment of keloid are still largely unknown, and it is essential to develop an objective assessment of keloid severity to evaluate the therapeutic response. We previously reported that our diffuse reflectance spectroscopy (DRS) system could assist clinicians in understanding the functional and structural condition of keloid scars. The purpose of this study was to understand clinical applicability of our DRS system on evaluating the scar severity and therapeutic response of keloid. We analyzed 228 spectral data from 71 subjects with keloid scars. The scars were classified into mild (0-3), moderate (4-7) and severe (8-11) according to the Vancouver scar scale. We found that as the severity of the scar increased, collagen concentration and water content increased, and the reduced scattering coefficient at 800 nm and oxygen saturation (SaO2) decreased. Using the DRS system, we found that collagen bundles aligned in a specific direction in keloid scars, but not in normal scars. Water content and SaO2 may be utilized as reliable parameters for evaluating the therapeutic response of keloid. In conclusion, the results obtained here suggest that the DRS has potential as an objective technique with which to evaluate keloid scar severity. In addition, it may be useful as a tool with which to track longitudinal response of scars in response to various therapeutic interventions.

Reliable recovery of the optical properties of multi-layer turbid media by iteratively using a layered diffusion model at multiple source-detector separations.

Accurately determining the optical properties of multi-layer turbid media using a layered diffusion model is often a difficult task and could be an ill-posed problem. In this study, an iterative algorithm was proposed for solving such problems. This algorithm employed a layered diffusion model to calculate the optical properties of a layered sample at several source-detector separations (SDSs). The optical properties determined at various SDSs were mutually referenced to complete one round of iteration and the optical properties were gradually revised in further iterations until a set of stable optical properties was obtained. We evaluated the performance of the proposed method using frequency domain Monte Carlo simulations and found that the method could robustly recover the layered sample properties with various layer thickness and optical property settings. It is expected that this algorithm can work with photon transport models in frequency and time domain for various applications, such as determination of subcutaneous fat or muscle optical properties and monitoring the hemodynamics of muscle.