Ascorbic Acid-Assisted Synthesis of Mesoporous Sodium Vanadium Phosphate Nanoparticles with Highly sp(2) -Coordinated Carbon Coatings as Efficient Cathode Materials for Rechargeable Sodium-Ion Batteries.

Herein, mesoporous sodium vanadium phosphate nanoparticles with highly sp(2) -coordinated carbon coatings (meso-Na3 V2 (PO4 )3 /C) were successfully synthesized as efficient cathode material for rechargeable sodium-ion batteries by using ascorbic acid as both the reductant and carbon source, followed by calcination at 750 °C in an argon atmosphere. Their crystalline structure, morphology, surface area, chemical composition, carbon nature and amount were systematically explored. Following electrochemical measurements, the resultant meso-Na3 V2 (PO4 )3 /C not only delivered good reversible capacity (98 mAh g(-1) at 0.1 A g(-1) ) and superior rate capability (63 mAh g(-1) at 1 A g(-1) ) but also exhibited comparable cycling performance (capacity retention: ≈74 % at 450 cycles at 0.4 A g(-1) ). Moreover, the symmetrical sodium-ion full cell with excellent reversibility and cycling stability was also achieved (capacity retention: 92.2 % at 0.1 A g(-1) with 99.5 % coulombic efficiency after 100 cycles). These attributes are ascribed to the distinctive mesostructure for facile sodium-ion insertion/extraction and their continuous sp(2) -coordinated carbon coatings, which facilitate electronic conduction.

Combined Experimental and Computational Studies of a Na2 Ni1-x Cux Fe(CN)6 Cathode with Tunable Potential for Aqueous Rechargeable Sodium-Ion Batteries.

Herein, potential-tunable Na2 Ni1-x Cux Fe(CN)6 nanoparticles with three-dimensional frameworks and large interstitial spaces were synthesized as alternative cathode materials for aqueous sodium-ion batteries by controlling the molar ratio of Ni(II) to Cu(II) at ambient temperature. The influence of the value of x on the crystalline structure, lattice parameters, electrochemical properties, and charge transfer of the resultant compound was explored by using powder X-ray diffractometry, density functional theory, cyclic voltammetry, galvanostatic charge-discharge techniques, and Bader charge analysis. Of the various formulations investigated, that with x=0.25 delivered the highest reversible capacity, superior rate capability, and outstanding cycling performance. These attributes are ascribed to its unique face-centered cubic structure for facile sodium-ion insertion/extraction and the strong interactions between Cu and N atoms, which promote structural stability.

The association between working memory precision and the nonlinear dynamics of frontal and parieto-occipital EEG activity.

Electrophysiological working memory (WM) research shows brain areas communicate via macroscopic oscillations across frequency bands, generating nonlinear amplitude modulation (AM) in the signal. Traditionally, AM is expressed as the coupling strength between the signal and a prespecified modulator at a lower frequency. Therefore, the idea of AM and coupling cannot be studied separately. In this study, 33 participants completed a color recall task while their brain activity was recorded through EEG. The AM of the EEG data was extracted using the Holo-Hilbert spectral analysis (HHSA), an adaptive method based on the Hilbert-Huang transforms. The results showed that WM load modulated parieto-occipital alpha/beta power suppression. Furthermore, individuals with higher frontal theta power and lower parieto-occipital alpha/beta power exhibited superior WM precision. In addition, the AM of parieto-occipital alpha/beta power predicted WM precision after presenting a target-defining probe array. The phase-amplitude coupling (PAC) between the frontal theta phase and parieto-occipital alpha/beta AM increased with WM load while processing incoming stimuli, but the PAC itself did not predict the subsequent recall performance. These results suggest frontal and parieto-occipital regions communicate through theta-alpha/beta PAC. However, the overall recall precision depends on the alpha/beta AM following the onset of the retro cue.

A holo-spectral EEG analysis provides an early detection of cognitive decline and predicts the progression to Alzheimer's disease.

Aims: Our aim was to differentiate patients with mild cognitive impairment (MCI) and Alzheimer's disease (AD) from cognitively normal (CN) individuals and predict the progression from MCI to AD within a 3-year longitudinal follow-up. A newly developed Holo-Hilbert Spectral Analysis (HHSA) was applied to resting state EEG (rsEEG), and features were extracted and subjected to machine learning algorithms. Methods: A total of 205 participants were recruited from three hospitals, with CN (n = 51, MMSE > 26), MCI (n = 42, CDR = 0.5, MMSE ≥ 25), AD1 (n = 61, CDR = 1, MMSE < 25), AD2 (n = 35, CDR = 2, MMSE < 16), and AD3 (n = 16, CDR = 3, MMSE < 16). rsEEG was also acquired from all subjects. Seventy-two MCI patients (CDR = 0.5) were longitudinally followed up with two rsEEG recordings within 3 years and further subdivided into an MCI-stable group (MCI-S, n = 36) and an MCI-converted group (MCI-C, n = 36). The HHSA was then applied to the rsEEG data, and features were extracted and subjected to machine-learning algorithms. Results: (a) At the group level analysis, the HHSA contrast of MCI and different stages of AD showed augmented amplitude modulation (AM) power of lower-frequency oscillations (LFO; delta and theta bands) with attenuated AM power of higher-frequency oscillations (HFO; beta and gamma bands) compared with cognitively normal elderly controls. The alpha frequency oscillation showed augmented AM power across MCI to AD1 with a reverse trend at AD2. (b) At the individual level of cross-sectional analysis, implementation of machine learning algorithms discriminated between groups with good sensitivity (Sen) and specificity (Spec) as follows: CN elderly vs. MCI: 0.82 (Sen)/0.80 (Spec), CN vs. AD1: 0.94 (Sen)/0.80 (Spec), CN vs. AD2: 0.93 (Sen)/0.90 (Spec), and CN vs. AD3: 0.75 (Sen)/1.00 (Spec). (c) In the longitudinal MCI follow-up, the initial contrasted HHSA between MCI-S and MCI-C groups showed significantly attenuated AM power of alpha and beta band oscillations. (d) At the individual level analysis of longitudinal MCI groups, deploying machine learning algorithms with the best seven features resulted in a sensitivity of 0.9 by the support vector machine (SVM) classifier, with a specificity of 0.8 yielded by the decision tree classifier. Conclusion: Integrating HHSA into EEG signals and machine learning algorithms can differentiate between CN and MCI as well as also predict AD progression at the MCI stage.

Catalytically Active Site Identification of Molybdenum Disulfide as Gas Cathode in a Nonaqueous Li-CO2 Battery.

Li-CO2 batteries have recently attracted attention as promising candidates for next-generation energy storage devices due to their extremely high theoretical energy density. The real application of Li-CO2 cells involves addressing several drawbacks, including high charging potential, poor coulombic efficiency, and low rechargeability. Molybdenum disulfide supported on carbon nanotubes (MoS2/CNT) with various ratios functioned as a cathode catalyst for Li-CO2 batteries. The optimal MoS2/CNT composite achieved a maximum discharge capacity of 8551 mAh g-1 with a coulombic efficiency of 96.7%. This hybrid also obtained an initial charging plateau of 3.87 V at a current density of 100 mA g-1 with a cutoff capacity of 500 mAh g-1. It provided ideal electrochemical stability of 142 cycles at the current densities of 100 mA g-1, which was comparable with that of some precious metal catalysts. This optimized MoS2/CNT was also cycled at 200 and 400 mA g-1 for 112 and 55 times, respectively. Density functional theory calculations demonstrated that the sulfided Mo-edge (s-Mo-edge) on MoS2 materials showed appropriate adsorption strengths of Li, CO2, and Li2CO3. Moreover, joint results of Raman profiles and extended X-ray absorption fine structure spectra elucidated that the catalytic efficiencies of MoS2/CNT hybrids were proportional to the quantities of exposed s-Mo-edge active sites.

Unraveling nonlinear electrophysiologic processes in the human visual system with full dimension spectral analysis.

Natural sensory signals have nonlinear structures dynamically composed of the carrier frequencies and the variation of the amplitude (i.e., envelope). How the human brain processes the envelope information is still poorly understood, largely due to the conventional analysis failing to quantify it directly. Here, we used a recently developed method, Holo-Hilbert spectral analysis, and steady-state visually evoked potential collected using electroencephalography (EEG) recordings to investigate how the human visual system processes the envelope of amplitude-modulated signals, in this case with a 14 Hz carrier and a 2 Hz envelope. The EEG results demonstrated that in addition to the fundamental stimulus frequencies, 4 Hz amplitude modulation residing in 14 Hz carrier and a broad range of carrier frequencies covering from 8 to 32 Hz modulated by 2 Hz amplitude modulation are also found in the two-dimensional frequency spectrum, which have not yet been recognized before. The envelope of the stimulus is also found to dominantly modulate the response to the incoming signal. The findings thus reveal that the electrophysiological response to amplitude-modulated stimuli is more complex than could be revealed by, for example, Fourier analysis. This highlights the dynamics of neural processes in the visual system.

A convenient phase transfer protocol to functionalize gold nanoparticles with short alkylamine ligands.

HYPOTHESIS: Aqueous citrate-stabilized gold nanoparticles (Au NPs) cannot be directly transferred from water to an immiscible organic solution using short alkyl ligands. However, Au NPs can be transferred from water to a water-organic interface if chemical and mechanical inputs are used to modify the interfacial energy and interfacial area. Ligand exchange can then take place at this interface. After separating the particles from the liquids, they can be transferred to a different organic phase. EXPERIMENTS: Hexane, alkylamine, and acetone were added to aqueous citrate-stabilized Au NPs to form a film at the system interfaces. After removing the liquid phases, Au NPs were readily redispersed into tetrahydrofuran (THF). The size and shape of the transferred Au NPs were evaluated by transmission electron microscopy (TEM) and small angle X-ray scattering (SAXS). FINDINGS: Au NPs with 13nm diameter are readily segregated from water with the aid of short alkylamine ligands. They form a thin film at the water/organic solvent interface, rendering them easy to separate from the liquid phases and possible to redisperse into another organic solvent. After the phase transfer process, Au NPs were functionalized with short amine ligands. In addition, the shape and size of Au NPs were preserved. The short amine-protected Au NPs in THF can stay stable for up to 27days or longer.

Ternary Spinel MCo2O4 (M = Mn, Fe, Ni, and Zn) Porous Nanorods as Bifunctional Cathode Materials for Lithium-O2 Batteries.

The development of Li-O2 battery electrocatalysts has been extensively explored recently. The Co3O4 oxide has attracted much attention because of its bifunctional activity and high abundance. In the present study, toxic Co(2+) has been replaced through the substitution on the tetrahedral spinel A site ions with environmental friendly metals (Mn(2+), Fe(2+), Ni(2+), and Zn(2+)), and porous nanorod structure are formed. Among these spinel MCo2O4 cathodes, the FeCo2O4 surface has the highest Co(3+) ratio. Thus, oxygen can be easily adsorbed onto the active sites. In addition, Fe(2+) in the tetrahedral site can easily release electrons to reduce oxygen and oxidize to half electron filled Fe(3+). The FeCo2O4 cathode exhibits the highest discharging plateau and lowest charging plateau as shown by the charge-discharge profile. Moreover, the porous FeCo2O4 nanorods can also facilitate achieving high capacity and good cycling performance, which are beneficial for O2 diffusion channels and Li2O2 formation/decomposition pathways.

Photoinduced atom-transfer cyclization of alpha-iodocycloalkanones bearing an allenyl side chain.

[reaction: see text] Irradiation of alpha-iodocycloalkanones bearing an allenyl side chain with a sunlamp effected atom-transfer cyclization to give cyclized products in good yield. A mechanism, involving radical atom-transfer cyclization accompanied by 1,5- and 1,4-hydrogen transfers, is proposed.

Complete corrosion inhibition through graphene defect passivation.

Graphene is expected to enable superior corrosion protection due to its impermeability and chemical inertness. Previous reports, however, demonstrate limited corrosion inhibition and even corrosion enhancement of graphene on metal surfaces. To enable the reliable and complete passivation, the origin of the low inhibition efficiency of graphene was investigated. Combining electrochemical and morphological characterization techniques, nanometer-sized structural defects in chemical vapor deposition grown graphene were found to be the cause for the limited passivation effect. Extremely fast mass transport on the order of meters per second both across and parallel to graphene layers results in an inhibition efficiency of only ∼50% for Cu covered with up to three graphene layers. Through selective passivation of the defects by atomic layer deposition (ALD) an enhanced corrosion protection of more than 99% was achieved, which compares favorably with commercial corrosion protection methods.

Mesoporous ZnCo2O4 nanoflakes with bifunctional electrocatalytic activities toward efficiencies of rechargeable lithium-oxygen batteries in aprotic media.

This study reports the successful synthesis of ternary spinel-based ZnCo2O4 nanoflakes (NFs) with mesoporous architectures via the combination of a urea-assisted hydrothermal reaction with calcination in an air atmosphere. Owing to their favorable mesostructures and desirable bifunctional oxygen reduction and evolution activities, the resulting mesoporous ZnCo2O4 NFs yielded stable cyclability at a cut-off capacity of 500 mA h gcarbon(-1) in the case of aprotic Li-O2 batteries.

Influence of sodium halides (NaF, NaCl, NaBr, NaI) on the photocatalytic performance of hydrothermally synthesized hematite photoanodes.

It has been suggested that a high concentration of Fe(3+) in solution, a low pH, and noncomplexing ions of high ionic strength are all essential for developing a high-quality hematite array. Our curiosity was piqued regarding the role of the electrolyte ions in the hydrothermal synthesis of hematite photoanodes. In this study, we prepared hematite photoanodes hydrothermally from precursor solutions of 0.1 M FeCl3 at pH 1.55 with a background electrolyte of 1.0 M sodium halide (NaF, NaCl, NaBr, or NaI). We compared the structures and properties of the as-obtained hematite photoanodes with those of the material prepared in 1.0 M NaNO3, the most widely adopted electrolyte in previous studies. Among our studied systems, we found that the hematite photoanode prepared in NaCl solution was the only one possessing properties similar to those of the sample obtained from the NaNO3 solution-most importantly in terms of photoelectrochemical performance (ca. 0.2 mA/cm(2) with +0.4 V vs SCE). The hematites obtained from the NaF, NaBr, and NaI solutions exhibited much lower (by approximately 2 orders of magnitude) photocurrent densities under the same conditions, possibly because of their relatively less ordered crystallinity and the absence of rodlike morphologies. Because the synthetic protocol was identical in each case, we believe that these two distinct features reflect the environments in which these hematite photoanodes were formed. Consistent with the latest studies reported in the literature of the X-ray photoelectron spectra of fast-frozen hematite colloids in aqueous solutions, it appears that the degree of surface ion loading at the electrolyte-hematite interface (Stern layer) is critical during the development of hematite photoanodes. We suspect that a lower ion surface loading benefits the hematite developing relatively higher-order and a rodlike texture, thereby improving the photoelectrochemical activity.

Photocatalytic CdSe QDs-decorated ZnO nanotubes: an effective photoelectrode for splitting water.

Arrays of ZnO nanorods (NRs) were successfully converted into nanotubes (NTs), used as photoelectrodes in photoelectrochemical (PEC) cells after their sensitization with CdSe quantum dots (QDs) and a strong correlation between the PEC performance and geometrical structure of ZnO NTs@CdSe(QDs) and ZnO NRs@CdSe(QDs) was established under the same conditions.

The first total synthesis of xenitorins B and C: assignment of absolute configuration.

Starting from (-)-beta-pinene, the first total synthesis of xenitorins B and C has been accomplished, which also allowed the assignment of their absolute configuration.