Dynamic orbital hybridization triggered spin-disorder renormalization via super-exchange interaction for oxygen evolution reaction.

The oxygen evolution reaction (OER) underpins many aspects of energy storage and conversion in modern industry and technology, but which still be suffering from the dilemma of sluggish reaction kinetics and poor electrochemical performance. Different from the viewpoint of nanostructuring, this work focuses on an intriguing dynamic orbital hybridization approach to renormalize the disordering spin configuration in porous noble-metal-free metal-organic frameworks (MOFs) to accelerate the spin-dependent reaction kinetics in OER. Herein, we propose an extraordinary super-exchange interaction to reconfigure the domain direction of spin nets at porous MOFs through temporarily bonding with dynamic magnetic ions in electrolytes under alternating electromagnetic field stimulation, in which the spin renormalization from disordering low-spin state to high-spin state facilitates rapid water dissociation and optimal carrier migration, leading to a spin-dependent reaction pathway. Therefore, the spin-renormalized MOFs demonstrate a mass activity of 2,095.1 A gmetal-1 at an overpotential of 0.33 V, which is about 5.9 time of pristine ones. Our findings provide a insight into reconfiguring spin-related catalysts with ordering domain directions to accelerate the oxygen reaction kinetics.

Dynamic repulsive interaction enables an asymmetric electron-phonon coupling for improving Raman scattering.

Two-dimensional (2D) materials are an excellent platform for surface-enhanced Raman spectroscopy (SERS). For ReS2, the Raman enhancement effect can be highly improved through the dipole-dipole interactions and synergistic resonance effects in the phase-engineering ReS2 films. However, the performance of the substrate can be improved further through regulating the electronic interaction between the ReS2 and probe molecules. Herein, a dynamic coulomb repulsion strategy is proposed to trigger an electronic state redistribution by asymmetric electrostatic interactions. With the phase-engineering ReS2/graphene heterostructure as a prototype, under laser excitation, the generated hot electrons in graphene and ReS2 can repel each other due to Coulomb interaction, which breaks the symmetrical distribution of hot electrons in ReS2, and increases the electronic concentration at the interface between ReS2 and the probe molecule. With R6G as the probe molecule, the asymmetric electron distribution and synergistic resonance effects on their interface improve the limit of detection to 10-12 M with an EF of 2.15 × 108. Meanwhile, the heterostructure also shows good uniformity, stability as well as unique anisotropy. This strategy can be generalized to other 2D heterostructures to obtain the ultrasensitive SERS substrates.

Zinc-doped C4N3/BiOBr S-scheme heterostructured hollow spheres for efficient photocatalytic degradation of tetracycline.

Photocatalytic degradation of organic pollutants in water is of great significance to the sustainable development of the environment, but encounters limited efficiency when a single compound is used. Thus, there have been enormous efforts to find novel photocatalytic heterostructured composites with high performance. In this work, a novel S-scheme heterostructure is constructed with BiOBr and Zn2+ doped C4N3 (Zn-C4N3) by a solvothermal method for efficient photodegradation of tetracycline (TC), a residual antibiotic difficult to be removed from the aquatic environment. Thanks to Zn2+-doping induced improvement in chemical affinity between Zn-C4N3 and BiOBr, well-formed Zn-C4N3/BiOBr heterostructured hollow spheres are formed. This structure can efficiently suppress fast recombination of photogenerated electron-hole pairs to enhance the photocatalytic activity of BiOBr dramatically. At a room temperature of 25 °C and neutral pH 7, the catalyst can degrade a significant portion of TC pollutants within 30 min under visible light. Also, the Zn-C4N3/BiOBr heterostructure displays good stability after recycling experiments. Free radical capture experiments and ESR tests show that ˙O2- is the main active substance for photocatalytic degradation of TC. This study provides new insights for constructing heterostructures with an intimate interface between the two phases for photocatalytic applications.

Ceftriaxone improves impairments in synaptic plasticity and cognitive behavior in APP/PS1 mouse model of Alzheimer's disease by inhibiting extrasynaptic NMDAR-STEP61 signaling.

Abnormal activation of the extrasynaptic N-methyl-d-aspartate receptor (NMDAR) contributes to the pathogenesis of Alzheimer's disease (AD). Ceftriaxone (Cef) can improve cognitive impairment by upregulating glutamate transporter-1 and promoting the glutamate-glutamine cycle in an AD mouse model. This study aimed to investigate the effects of Cef on synaptic plasticity and cognitive-behavioral impairment and to unravel the associated underlying mechanisms. We used an APPswe/PS1dE9 (APP/PS1) mouse model of AD in this study. Extrasynaptic components from hippocampal tissue homogenates were isolated using density gradient centrifugation. Western blot was performed to evaluate the expressions of extrasynaptic NMDAR and its downstream elements. Intracerebroventricular injections of adeno-associated virus (AAV)-striatal enriched tyrosine phosphatase 61 (STEP61 ) and AAV-STEP61 -shRNA were used to modulate the expressions of STEP61 and extrasynaptic NMDAR. Long-term potentiation (LTP) and Morris water maze (MWM) tests were performed to evaluate the synaptic plasticity and cognitive function. The results showed that the expressions of GluN2B and GluN2BTyr1472 in the extrasynaptic fraction were upregulated in AD mice. Cef treatment effectively prevented the upregulation of GluN2B and GluN2BTyr1472 expressions. It also prevented changes in the downstream signals of extrasynaptic NMDAR, including increased expressions of m-calpain and phosphorylated p38 MAPK in AD mice. Furthermore, STEP61 upregulation enhanced, whereas STEP61 downregulation reduced the Cef-induced inhibition of the expressions of GluN2B, GluN2BTyr1472 , and p38 MAPK in the AD mice. Similarly, STEP61 modulation affected Cef-induced improvements in induction of LTP and performance in MWM tests. In conclusion, Cef improved synaptic plasticity and cognitive behavioral impairment in APP/PS1 AD mice by inhibiting the overactivation of extrasynaptic NMDAR and STEP61 cleavage due to extrasynaptic NMDAR activation.

Significantly increased Raman enhancement enabled by hot-electron-injection-induced synergistic resonances on anisotropic ReS2 films.

Two-dimensional (2D) materials are an excellent platform for surface-enhanced Raman spectroscopy (SERS). However, a poor detection sensitivity hinders their practical application. Exciton resonance (µex) can improve SERS significantly by lending intensity to nearby charge-transfer resonance. Coincidentally, for ReS2, the enhanced µex can be achieved through the injection of excited-state electrons which can adjust the energy band to the SERS detection range. Moreover, ReS2 has strong anisotropic properties, which adds an additional dimension for SERS. Therefore, ReS2 is an ideal candidate to realize highly sensitive anisotropic SERS. In this paper, the metallic T phase of ReS2 is introduced to the semiconducting Td phase by phase engineering. The photoinduced electron tunneling from the T phase to the Td phase can tune exciton emissions to the visible region, which effectively facilitates the photoinduced charge transfer processes. With RhB as the probe molecule, the synergistic resonance effects improve the limit of detection to 10-9 M with the enhancement factor up to about 108. Meanwhile, the obtained ultrasensitive SERS substrates also show good uniformity, stability as well as unique anisotropy. Our results open a new perspective in the improvement of the SERS performance.

Light-driven Orderly Assembly of Ir-atomic Chains to Integrate a Dynamic Reaction Pathway for Acidic Oxygen Evolution.

This work suggests an intriguing light-driven atomic assembly proposal to orderly configure the distribution of reactive sites to optimize the spin-entropy-related orbital interaction and charge transfer from electrocatalysts to intermediates. Herein, the introduced fluorine (F) atoms acting as photo-corrosion centres in MnO1.9 F0.1 effectively soften the bonding interaction of Mn-O bonds in the IrCl3 solution. Therefore, partial Mn atoms can be successively replaced to form orderly atomic-hybridized catalysts with a spin-related low entropy due to the coexistence of Ir-atomic chains and clusters. The time-related elemental analysis demonstrates that the dynamic dissolution/redeposition of Ir clusters in acidic oxygen evolution leads to a reintegration of the reaction pathway to seek the switchable rate-limiting step with a lower activation energy.

Asymmetric Exchange Interaction Induces Highly Efficient Alkaline Hydrogen Evolution in RhFe Bimetallene.

An RhFe bimetallene with Fe atoms doped into Rh host for efficient hydrogen evolution reaction (HER), is constructed. When two doped Fe atoms occupy neighboring asymmetric spatial positions, their asymmetric exchange interaction drives electron hopping between the dxy orbital of a Fe atom and the dz 2 orbital of its neighboring Fe atom to push the d band center closer to the Fermi level as a result of electronic state reconstruction. The designed bimetallene with thickness of 0.77 nm (5 atomic layers), possesses excellent HER performance. The low overpotentials of 24.4 and 34.6 mV are achieved at the 10 and 100 mA cm-2 current densities in 1 m KOH solution, respectively. An ultra-low Tafel slope of 8.9 mV dec-1 shows that this kind of RhFe bimetallene is of an ultrafast kinetic process. This work provides a strategy for designing HER catalysts with double metal composites.

The exchange between anions and cations induced by coupled plasma and thermal annealing treatment for room-temperature ferromagnetism.

Two-dimensional (2D) materials, with outstanding magnetic properties at room temperature, are highly desirable for the future spintronic and nanoscale electronic industry. However, most of the 2D systems are not of magnetic nature due to thermal fluctuations. Herein, we propose a novel strategy to induce robust room-temperature ferromagnetism in the originally nonmagnetic 2D ReS2 by the exchange between anions and cations. The vacancies are created by argon plasma treatment, which lowers the formation energy of point defects. The subsequent annealing facilitates the movement of the cations into the anion sites, giving rise to antisite defects, which leads to a significant increase in the magnetization. First-principles calculations demonstrate that the point defect with respect to the antisite substitution from Re to S is responsible for the extraordinary room-temperature ferromagnetism. This work opens a new door to the design of spin electronic structures by controllable antisite defects.

Integrated Spatial Modulation and STBC-VBLAST Design toward Efficient MIMO Transmission.

In this contribution, the concept of spatial modulation (SM) is firstly integrated into the structure of space-time block codes (STBC)-aided vertical Bell-labs layered space-time (VBLAST) systems, in order to strike a balanced tradeoff among bit error ratio (BER), spectral efficiency and computational complexity. First of all, in order to enhance the BER performance of STBC-VBLAST, we advocate an effective transmit power allocation (TPA) scheme with negligible implementation costs, while dividing the STBC and VBLAST layers with alleviated interference, so as to facilitate combination with SM. Then, we further utilize the unique structure of SM for enhancing the spectral efficiency of original STBC-VBLAST, wherein the information is conveyed by not only the amplitude/phase modulation (APM) symbols but also the antenna indices. In addition, constellation sets of STBC symbols are specifically designed to be rotated to make full use of the degrees of freedom. Finally, the performance advantages of the above-mentioned structures over traditional STBC-VBLAST are demonstrated by the theoretical derivation of a closed-form expression for the union bound on the bit error probability for various spectral efficiencies, and they are supported by simulation results.

Recharged Catalyst with Memristive Nitrogen Reduction Activity through Learning Networks of Spiking Neurons.

Electrocatalysis from N2 to NH3 has been increasingly studied because it provides an environmentally friendly avenue to take the place of the current Haber-Bosch method. Unfortunately, the conversion of N2 to NH3 is far below the necessary level for implementation at a large scale. Inspired by signal memory in a spiking neural network, we developed rechargeable catalyst technology to activate and remember the optimal catalytic activity using manageable electrical stimulation. Herein, we designed double-faced FeReS3 Janus layers that mimic a multiple-neuron network consisting of resistive switching synapses, enabling a series of intriguing multiphase transitions to activate undiscovered catalytic activity; the activation energy barrier is clearly reduced via an active site conversion between two nonequivalent surfaces. Electrical field-stimulated FeReS3 demonstrates a Faradaic efficiency of 43% and the highest rate of 203 µg h-1 mg-1 toward NH3 synthesis. Moreover, this rechargeable catalyst displays unprecedented catalytic performance that persists for up to 216 h and can be repeatedly activated through a simple charging operation.

Sulbactam improves binding property and uptake capacity of glutamate transporter-1 and decreases glutamate concentration in the CA1 region of hippocampus of global brain ischemic rats.

Glutamate transporter-1 (GLT-1) removes most glutamate in the synaptic cleft. Sulbactam confers neuronal protection against ischemic insults in the hippocampal CA1 region accompanied by the upregulation of GLT-1 expression in rats. The present study further investigates the effect of sulbactam on the binding property and uptake capacity of GLT-1 for glutamate, and the change in extracellular glutamate concentration in the hippocampal CA1 region of rats with global brain ischemia. The binding property and uptake capacity of GLT-1 were measured using a radioligand binding and uptake assay, respectively, with L-3H-glutamate. The extracellular glutamate concentration was detected using microdialysis and high-performance liquid chromatography-mass spectrometry. Neuropathological evaluation was performed based on thionin staining. It was shown that sulbactam pre-treatment changed GLT-1 binding property, including increased Bmax and decreased Kd values, increased GLT-1 uptake capacity for glutamate, and inhibited the elevation of extracellular glutamate concentration in rats with global cerebral ischemia. These effects of sulbactam were accompanied by its neuronal protection on the hippocampal CA1 neurons against delayed neuronal death resulted from ischemic insult. Furthermore, administration of GLT-1 antisense oligodeoxynucleotides, which inhibited the expression of GLT-1, blocked the aforementioned sulbactam-related effects, which suggested that GLT-1 upregulation mediated the above effect although other mechanisms independent of the upregulation of GLT-1 expression could not be excluded. It could be concluded that sulbactam improves the binding property and uptake capacity of GLT-1 for glutamate and then reduces the glutamate concentration and excitotoxicity during global cerebral ischemia, which contributes to the neuroprotection of sulbactam against brain ischemia.

Dual-metal-driven Selective Pathway of Nitrogen Reduction in Orderly Atomic-hybridized Re2MnS6 Ultrathin Nanosheets.

The future of sustainable fertilizers and carbon-free energy carrier demands innovative breakthroughs in the exploitation of efficient electrocatalysts for synthesizing ammonia (NH3) from nitrogen (N2) in mild conditions. Understanding and regulating the reaction intermediates that form on the catalyst surface through careful catalyst design could bypass certain limitations associated with ambiguous adsorbate evolution mechanism. Herein, we propose ternary intermetallic Re2MnS6 ultrathin nanosheets that include orderly hybridized Mn-Re dual-metal sites through strong Hubbard e-e interaction, demonstrating a promising selectivity toward reaction process from N2 to NH3. The ordered inclusion of Mn sites leads to a structural phase transition and appearance of nonbonding semimetal states, in which the rate-limiting activation energy barrier is significantly decreased through a conversion in reaction pathway. As a result, the performance of N2 reduction in Re2MnS6 is increased about 6.6 times compared to the single-metal ReS2.

Self-Assembly of Porphyrin-Based Metallacages into Octahedra.

Despite rapid progress in recent years, it has remained challenging to prepare well-defined metal-organic complex-based suprastructures. As a result, the physicochemical mechanisms leading to their geometrical complexity remain perplexing. Here, a porphyrin-based metallacage was used as a building block to construct octahedra via self-assembly, and the mechanism for the evolution of the metallacages into octahedra was disclosed by both experiments and theoretical simulations.

Resorcinarene Induced Assembly of Carotene and Lutein into Hierarchical Superstructures.

The manipulation of carotenoid-based hierarchical superstructures affords attractive properties that facilitate application in biology and photosynthesis. Here, tubular suprastructures formed from water-soluble amide-modified resorcinarene and ß-carotene were reported, whereas microsheets were formed when ß-carotene was replaced with lutein. These structures were characterized using various measurements, indicating the differences of binding sites between resorcinarene and ß-carotene/lutein. Subsequently, the assembly mechanism was described by calculating the formation energy of the assemblies.

Constructing Asymmetrical Ni-Centered {NiN2O4} Octahedra in Layered Metal-Organic Structures for Near-Room-Temperature Single-Phase Magnetoelectricity.

Layered metal-organic structures (LMOSs) as magnetoelectric (ME) multiferroics have been of great importance for realizing new functional devices in nanoelectronics. Until now, however, achieving such room-temperature and single-phase ME multiferroics in LMOSs have proven challenging due to low transition temperature, poor spontaneous polarization, and weak ME coupling effect. Here, we demonstrate the construction of a LMOS in which four Ni-centered {NiN2O4} octahedra form in layer with asymmetric distortions using the coordination bonds between diphenylalanine molecules and transition metal Ni(II). Near room-temperature (283 K) ferroelectricity and ferromagnetism are observed to be both spontaneous and hysteretic. Particularly, the multiferroic LMOS exhibits strong magnetic-field-dependent ME polarization with low-magnetic-field control. The change in ME polarization with increasing applied magnetic field µ0H from 0 to 2 T decreases linearly from 0.041 to 0.011 µC/cm2 at the strongest ME coupling temperature of 251 K. The magnetic domains can be manipulated directly by applied electric field at 283 K. The asymmetrical distortion of Ni-centered octahedron in layer spurs electric polarization and ME effect and reduces spin frustration in the octahedral geometry due to spin-charge-orbital coupling. Our results represent an important step toward the production of room-temperature single-phase organic ME multiferroics.

Triplet-Induced Lesion Formation at CpT and TpC Sites in DNA.

UV irradiation induces DNA lesions particularly at dipyrimidine sites. Using time-resolved UV pump (250 nm) and mid-IR probe spectroscopy the triplet pathway of cyclobutane pyrimidine dimer (CPD) formation within TpC and CpT sequences was studied. The triplet state is initially localized at the thymine base but decays with 30 ns under formation of a biradical state extending over both bases of the dipyrimidine. Subsequently this state either decays back to the electronic ground state on the 100 ns time scale or forms a cyclobutane pyrimidine dimer lesion (CPD). Stationary IR spectroscopy and triplet sensitization via 2'-methoxyacetophenone (2-M) in the UVA range shows that the lesions are formed with an efficiency of approximately 1.5 %. Deamination converts the cytosine moiety of the CPD lesions on the time scale of 10 hours into uracil which gives CPD(UpT) and CPD(TpU) lesions in which the coding potential of the initial cytosine base is vanished.

Oxygen-defect-dependent ferromagnetism and strain modulation in free-standing two-dimensional TiO2 monolayers.

Recently, layered two-dimensional titania (2D-TiO2) with a reduced band gap has been successfully synthesized. However, as an important application in spintronics, ferromagnetism in this material has not been investigated so far. To obtain the expected ferromagnetism, the formation and stability of the most prominent oxygen defects in a TiO2 monolayer under different external strains were explored systematically. The calculated results disclosed that structural deformation induced by tensile strain not only led to changes in the oxygen defect formation energy but also modified its magnetic features. With an increase in compressed strain, the Curie temperature in this system decreased due to insufficient spin polarization. Our calculations provide a strategy to utilize oxygen defect and strain engineering to realize applications of 2D TiO2 monolayers in spintronics.

Bright, stable, and tunable solid-state luminescence of carbon nanodot organogels.

Despite the sustained enthusiastic interest in fluorescent carbon nanodots (FCNDs), it is still challenging to achieve bright and widely tunable solid-state luminescence. Herein, organogels embedded with FCNDs were simply synthesized via a one-pot pyrolysis method. Subsequently, the excitation of a single ultraviolet (UV) excitation line results in tunable solid-state luminescence ranging from blue to red with quantum yields (QYs) >14%. In this study, N and S elements were co-doped to regulate the aggregation of FCNDs, which consequently modulated the Stokes shift of the photoluminescence (PL) by managing the degree of photon reabsorption. Notably, without compact aggregations, the dispersions of FCNDs in the organogel matrix indeed render bright fluorescence, which results from the suppression of excessive photon reabsorption and nonradiative resonant energy transfer (NRET).

Enhancement of Ferromagnetism in Nonmagnetic Metal Oxide Nanoparticles by Facet Engineering.

Ferromagnetism in semiconducting metal oxide nanoparticles has been intensively investigated due to their potential applications in spintronics, information storage, and biomedicine. Ferromagnetism can be produced in nonmagnetic metal oxide nanoparticles by a variety of methods or factors, but the saturated magnetization is typically of the order of 10-4 emu g-1 and too small to be useful in practice. In this work, it is demonstrated theoretically and experimentally that stronger ferromagnetism can be achieved in undoped nonmagnetic metal oxide semiconductors by exposing some specific polar crystal facets with carvings of special bonds via the interaction with underlying vacancies. In2 O3 microcubes with completely enclosed {001} polar facets show two orders of magnitude enhancement at room temperature compared to nanoparticles with an irregular morphology. The surface magnetic domains on the {001} facets account for the significantly enhanced ferromagnetism. The technique and concept described here can be extended to other types of metal oxide nanostructures to spur their application to spintronics.

2'-Methoxyacetophenone: An Efficient Photosensitizer for Cyclobutane Pyrimidine Dimer Formation.

Stationary and time-resolved experiments show that 2'-methoxyacetophenone (2-M) is an interesting compound for the investigation of triplet states in thymine samples. Time-resolved emission experiments show that the fluorescence lifetime of 2-M is 660 ps. A similar time constant of 680 ps is found in transient IR experiments. The data indicate efficient intersystem crossing (≈97%) from the fluorescent singlet state to the triplet state. The lifetime of the triplet state of 2-M dissolved in D2O at room temperature and ambient oxygen concentration is 400 ns. 2-M has a strong absorption in the UV-A range and can photosensitize the triplet state of a thymidine dinucleotide with light at a wavelength of 320 nm. The experiments show that 2-M is well-suited for time-resolved experiments on the triplet-sensitizing process.