Module-Designed Carbon-Coated Separators for High-Loading,High-Sulfur-Utilization Cathodes in Lithium–Sulfur Batteries

Lithium–sulfur batteries have great potential as next-generation energy-storage devices because of their high theoretical charge-storage capacity and the low cost of the sulfur cathode. To accelerate the development of lithium–sulfur technology, it is necessary to address the intrinsic material and extrinsic technological challenges brought about by the insulating active solid-state materials and the soluble active liquid-state materials. Herein, we report a systematic investigation of module-designed carbon-coated separators, where the carbon coating layer on the polypropylene membrane decreases the irreversible loss of dissolved polysulfides and increases the reaction kinetics of the high-loading sulfur cathode. Eight different conductive carbon coatings were considered to investigate how the materials’ characteristics contribute to the lithium–sulfur cell’s cathode performance. The cell with a nonporous-carbon-coated separator delivered an optimized peak capacity of 1112 mA∙h g⁻¹ at a cycling rate of C/10 and retained a high reversible capacity of 710 mA∙h g⁻¹ after 200 cycles under lean-electrolyte conditions. Moreover, we demonstrate the practical high specific capacity of the cathode and its commercial potential, achieving high sulfur loading and content of 4.0 mg cm⁻² and 70 wt%, respectively, and attaining high areal and gravimetric capacities of 4.45 mA∙h cm⁻² and 778 mA∙h g⁻¹, respectively.     

Efficient Photoelectrochemical Energy Conversion using Spinach Photosystem II (PSII) in Lipid Multilayer Films

The need for clean, renewable energy has fostered research into photovoltaic alternatives to silicon solar cells. Pigment–protein complexes in green plants convert light energy into chemical potential using redox processes that produce molecular oxygen. Here, we report the first use of spinach protein photosystem II (PSII) core complex in lipid films in photoelectrochemical devices. Photocurrents were generated from PSII in a ∼2 μm biomimetic dimyristoylphosphatidylcholine (DMPC) film on a pyrolytic graphite (PG) anode with PSII embedded in multiple lipid bilayers. The photocurrent was ∼20 μA cm⁻² under light intensity 40 mW cm⁻². The PSII–DMPC anode was used in a photobiofuel cell with a platinum black mesh cathode in perchloric acid solution to give an output voltage of 0.6 V and a maximum output power of 14 μW cm⁻². Part of this large output is related to a five-unit anode–cathode pH gradient. With catholytes at higher pH or no perchlorate, or using an MnO₂ oxygen-reduction cathode, the power output was smaller. The results described raise the possibility of using PSII–DMPC films in small portable power conversion devices.     

Hydrogen Bonding and Polymorphism of Amino Alcohol Salts with Quinaldinate: Structural Study

Three amino alcohols, 3-amino-1-propanol (abbreviated as 3a1pOH), 2-amino-1-butanol (2a1bOH), and 2-amino-2-methyl-1-propanol (2a2m1pOH), were reacted with quinoline-2-carboxylic acid, known as quinaldinic acid. This combination yielded three salts, (3a1pOHH)quin (1, 3a1pOHH⁺ = protonated 3-amino-1-propanol, quin⁻ = anion of quinaldinic acid), (2a1bOHH)quin (2, 2a1bOHH⁺ = protonated 2-amino-1-butanol), and (2a2m1pOHH)quin (3, 2a2m1pOHH⁺ = protonated 2-amino-2-methyl-1-propanol). The 2-amino-1-butanol and 2-amino-2-methyl-1-propanol systems produced two polymorphs each, labeled 2a/2b and 3a/3b, respectively. The compounds were characterized by X-ray structure analysis on single-crystal. The crystal structures of all consisted of protonated amino alcohols with NH₃⁺ moiety and quinaldinate anions with carboxylate moiety. The used amino alcohols contained one OH and one NH₂ functional group, both prone to participate in hydrogen bonding. Therefore, similar connectivity patterns were expected. This proved to be true to some extent as all structures contained the NH₃⁺∙∙∙⁻OOC heterosynthon. Nevertheless, different hydrogen bonding and π∙∙∙π stacking interactions were observed, leading to distinct connectivity motifs. The largest difference in hydrogen bonding occurred between polymorphs 3a and 3b, as they had only one heterosynton in common.     

The Effect of Growth Parameters on Electrophysical and Memristive Properties of Vanadium Oxide Thin Films

We have experimentally studied the influence of pulsed laser deposition parameters on the morphological and electrophysical parameters of vanadium oxide films. It is shown that an increase in the number of laser pulses from 10,000 to 60,000 and an oxygen pressure from 3 × 10⁻⁴ Torr to 3 × 10⁻² Torr makes it possible to form vanadium oxide films with a thickness from 22.3 ± 4.4 nm to 131.7 ± 14.4 nm, a surface roughness from 7.8 ± 1.1 nm to 37.1 ± 11.2 nm, electron concentration from (0.32 ± 0.07) × 10¹⁷ cm⁻³ to (42.64 ± 4.46) × 10¹⁷ cm⁻³, electron mobility from 0.25 ± 0.03 cm²/(V·s) to 7.12 ± 1.32 cm²/(V·s), and resistivity from 6.32 ± 2.21 Ω·cm to 723.74 ± 89.21 Ω·cm. The regimes at which vanadium oxide films with a thickness of 22.3 ± 4.4 nm, a roughness of 7.8 ± 1.1 nm, and a resistivity of 6.32 ± 2.21 Ω·cm are obtained for their potential use in the fabrication of ReRAM neuromorphic systems. It is shown that a 22.3 ± 4.4 nm thick vanadium oxide film has the bipolar effect of resistive switching. The resistance in the high state was (89.42 ± 32.37) × 10⁶ Ω, the resistance in the low state was equal to (6.34 ± 2.34) × 10³ Ω, and the ratio R_HRS/R_LRS was about 14,104. The results can be used in the manufacture of a new generation of micro- and nanoelectronics elements to create ReRAM of neuromorphic systems based on vanadium oxide thin films.     

Elucidation of Interaction between Whey Proteins and Proanthocyanidins and Its Protective Effects on Proanthocyanidins during In-Vitro Digestion and Storage

Whey proteins and oligomeric proanthocyanidins have nutritional value and are widely used in combination as food supplements. However, the effect of the interactions between proanthocyanidins and whey proteins on their stability has not been studied in depth. In this work, we aimed to characterize the interactions between β-Lactoglobulin (β-LG) and α-lactalbumin (α-LA) and oligomeric proanthocyanidins, including A1, A2, B1, B2, B3, and C1, using multi-spectroscopic and molecular docking methods. Fluorescence spectroscopic data revealed that all of the oligomeric proanthocyanidins quenched the intrinsic fluorescence of β-LG or α-LA by binding-related fluorescence quenching. Among the six oligomeric proanthocyanidins, A1 showed the strongest affinity for β-LG (K_a = 2.951 (±0.447) × 10⁴ L∙mol⁻¹) and α-LA (K_a = 1.472 (±0.236) × 10⁵ L∙mol⁻¹) at 297 K. β-LG/α-LA and proanthocyanidins can spontaneously form complexes, which are mainly induced by hydrophobic interactions, hydrogen bonds, and van der Waals forces. Fourier-transform infrared spectroscopy (FTIR) and circular dichroism spectroscopy showed that the secondary structures of the proteins were rearranged after binding to oligomeric proanthocyanidins. During in vitro gastrointestinal digestion, the recovery rate of A1 and A2 increased with the addition of WPI by 11.90% and 38.43%, respectively. The addition of WPI (molar ratio of 1:1) increased the retention rate of proanthocyanidins A1, A2, B1, B2, B3, and C1 during storage at room temperature by 14.01%, 23.14%, 30.09%, 62.67%, 47.92%, and 60.56%, respectively. These results are helpful for the promotion of protein–proanthocyanidin complexes as functional food ingredients in the food industry.     

Spectrophotometric Study of Bridging N-Donor Ligand-Induced Supramolecular Assembly of Conjugated Zn-Trisporphyrin with a Triphenylamine Core

This article studies the supramolecular assembly behavior of a Zn-trisporphyrin conjugate containing a triphenylamine core (1) with bridging N-donor ligands using the UV-vis spectrophotometric titration method at micromolar concentrations. Our results show that pyridine, a non-bridging ligand, formed a 3:1 open complex with 1. The corresponding binding constant was estimated to be (2.7 ± 0.15) × 10¹⁴ M⁻³. In contrast, bridging ligands, 4,4-bipyridine (BIPY) and 1,3-di(4-pyridyl)propane (DPYP), formed stable 3:2 double-decker complexes with 1 in solution, which collapsed to yield a 3:1 open complex when excess BIPY or DPYP was added. The binding constants for forming BIPY and DPYP double-decker complexes were estimated to be (9.26 ± 0.07) × 10²⁷ M⁻⁴ and (3.62 ± 0.16) × 10²⁷ M⁻⁴, respectively. The UV-vis titration profiles supported the conclusion that the degradation of the 3:2 double-decker 1∙BIPY complex is less favorable compared to that of 1∙DPYP. Consequently, the formation of the 3:1 1∙DPYP open complex proceeded more readily than that of 1∙BIPY.     

Computational Studies of Coinage Metal Anion M− + CH3X (X = F,Cl, Br,I) Reactions in Gas Phase

We characterized the stationary points along the nucleophilic substitution (S_N2), oxidative insertion (OI), halogen abstraction (XA), and proton transfer (PT) product channels of M⁻ + CH₃X (M = Cu, Ag, Au; X = F, Cl, Br, I) reactions using the CCSD(T)/aug-cc-pVTZ level of theory. In general, the reaction energies follow the order of PT > XA > S_N2 > OI. The OI channel that results in oxidative insertion complex [CH₃–M–X]⁻ is most exothermic, and can be formed through a front-side attack of M on the C-X bond via a high transition state OxTS or through a S_N2-mediated halogen rearrangement path via a much lower transition state invTS. The order of OxTS > invTS is inverted when changing M⁻ to Pd, a d¹⁰ metal, because the symmetry of their HOMO orbital is different. The back-side attack S_N2 pathway proceeds via typical Walden-inversion transition state that connects to pre- and post-reaction complexes. For X = Cl/Br/I, the invS_N2-TS’s are, in general, submerged. The shape of this M⁻ + CH₃X S_N2 PES is flatter as compared to that of a main-group base like F⁻ + CH₃X, whose PES has a double-well shape. When X = Br/I, a linear halogen-bonded complex [CH₃−X∙··M]⁻ can be formed as an intermediate upon the front-side attachment of M on the halogen atom X, and it either dissociates to CH₃ + MX⁻ through halogen abstraction or bends the C-X-M angle to continue the back-side S_N2 path. Natural bond orbital analysis shows a polar covalent M−X bond is formed within oxidative insertion complex [CH₃–M–X]⁻, whereas a noncovalent M–X halogen-bond interaction exists for the [CH₃–X∙··M]⁻ complex. This work explores competing channels of the M⁻ + CH₃X reaction in the gas phase and the potential energy surface is useful in understanding the dynamic behavior of the title and analogous reactions.     

Two-Dimensional TeB Structures with Anisotropic Carrier Mobility and Tunable Bandgap

Two-dimensional (2D) semiconductors with desirable bandgaps and high carrier mobility have great potential in electronic and optoelectronic applications. In this work, we proposed α-TeB and β-TeB monolayers using density functional theory (DFT) combined with the particle swarm-intelligent global structure search method. The high dynamical and thermal stabilities of two TeB structures indicate high feasibility for experimental synthesis. The electronic structure calculations show that the two structures are indirect bandgap semiconductors with bandgaps of 2.3 and 2.1 eV, respectively. The hole mobility of the β-TeB sheet is up to 6.90 × 10² cm² V⁻¹ s⁻¹. By reconstructing the two structures, we identified two new horizontal and lateral heterostructures, and the lateral heterostructure presents a direct band gap, indicating more probable applications could be further explored for TeB sheets.     

Synthesis,Structural and Physicochemical Characterization of a Titanium(IV) Compound with the Hydroxamate Ligand N,2-Dihydroxybenzamide

The siderophore organic ligand N,2-dihydroxybenzamide (H₂dihybe) incorporates the hydroxamate group, in addition to the phenoxy group in the ortho-position and reveals a very rich coordination chemistry with potential applications in medicine, materials, and physical sciences. The reaction of H₂dihybe with TiCl₄ in methyl alcohol and KOH yielded the tetranuclear titanium oxo-cluster (TOC) [Ti^IV₄(μ-O)₂(HOCH₃)₄(μ-Hdihybe)₄(Hdihybe)₄]Cl₄∙10H₂O∙12CH₃OH (1). The titanium compound was characterized by single-crystal X-ray structure analysis, ESI-MS, ¹³C, and ¹H NMR spectroscopy, solid-state and solution UV–Vis, IR vibrational, and luminescence spectroscopies and molecular orbital calculations. The inorganic core Ti₄(μ-O)₂ of 1 constitutes a rare structural motif for discrete Ti^IV₄ oxo-clusters. High-resolution ESI-MS studies of 1 in methyl alcohol revealed the presence of isotopic distribution patterns which can be attributed to the tetranuclear clusters containing the inorganic core {Ti₄(μ-O)₂}. Solid-state IR spectroscopy of 1 showed the presence of an intense band at ~800 cm⁻¹ which is absent in the spectrum of the H₂dihybe and was attributed to the high-energy ν(Ti₂–μ-O) stretching mode. The ν(C=O) in 1 is red-shifted by ~10 cm⁻¹, while the ν(N-O) is blue-shifted by ~20 cm⁻¹ in comparison to H₂dihybe. Density Functional Theory (DFT) calculations reveal that in the experimental and theoretically predicted IR absorbance spectra of the ligand and Ti-complex, the main bands observed in the experimental spectra are also present in the calculated spectra supporting the proposed structural model. ¹H and ¹³C NMR solution (CD₃OD) studies of 1 reveal that it retains its integrity in CD₃OD. The observed NMR changes upon addition of base to a CD₃OD solution of 1, are due to an acid–base equilibrium and not a change in the Ti^IV coordination environment while the decrease in the complex’s lability is due to the improved electron-donating properties which arise from the ligand deprotonation. Luminescence spectroscopic studies of 1 in solution reveal a dual narrow luminescence at different excitation wavelengths. The TOC 1 exhibits a band-gap of 1.98 eV which renders it a promising candidate for photocatalytic investigations.     

Pristine and Modified Porous Membranes for Zinc Slurry–Air Flow Battery

The membrane is a crucial component of Zn slurry–air flow battery since it provides ionic conductivity between the electrodes while avoiding the mixing of the two compartments. Herein, six commercial membranes (Cellophane™ 350PØØ, Zirfon^®, Fumatech^® PBI, Celgard^® 3501, 3401 and 5550) were first characterized in terms of electrolyte uptake, ion conductivity and zincate ion crossover, and tested in Zn slurry–air flow battery. The peak power density of the battery employing the membranes was found to depend on the in-situ cell resistance. Among them, the cell using Celgard^® 3501 membrane, with in-situ area resistance of 2 Ω cm² at room temperature displayed the highest peak power density (90 mW cm⁻²). However, due to the porous nature of most of these membranes, a significant crossover of zincate ions was observed. To address this issue, an ion-selective ionomer containing modified poly(phenylene oxide) (PPO) and N-spirocyclic quaternary ammonium monomer was coated on a Celgard^® 3501 membrane and crosslinked via UV irradiation (PPO-3.45 + 3501). Moreover, commercial FAA-3 solutions (FAA, Fumatech) were coated for comparison purpose. The successful impregnation of the membrane with the anion-exchange polymers was confirmed by SEM, FTIR and Hg porosimetry. The PPO-3.45 + 3501 membrane exhibited 18 times lower zincate ions crossover compared to that of the pristine membrane (5.2 × 10⁻¹³ vs. 9.2 × 10⁻¹² m² s⁻¹). With low zincate ions crossover and a peak power density of 66 mW cm⁻², the prepared membrane is a suitable candidate for rechargeable Zn slurry–air flow batteries.     

In silico design to enhance the barrier height for magnetization reversal in Dy(iii) sandwich complexes by stitching them under the umbrella of corannulene

Lanthanide based single molecular magnets (SMMs), particularly dysprocenium based SIMs, are well known for their high energy barrier for spin reversal (U_eff) and blocking temperatures (T_B). Enhancing these two parameters and at the same time obtaining ambient stability is key to realising end-user applications such as compact storage or as qubits in quantum computing. In this work, by employing an array of theoretical tools (DFT, ab initio CASSCF and molecular dynamics), we have modelled six complexes [(η⁵-corannulene)Dy(Cp)] (1), [(η⁵-corannulene)Dy(C₆H₆)] (2), [(η⁶-corannulene)Dy(Cp)] (3), [(η⁶-corannulene)Dy(C₆H₆)] (4), [(exo-η⁵-corannulene)Dy(endo-η⁵-corannulene)] (5), and [(endo-η⁵-corannulene)Dy(endo-η⁵-corannulene)] (6) containing corannulene as a capping ligand to stabilise Dy(iii) half-sandwich complexes. Our calculations predict a strong axiality exerted by the Dy–C interactions in all complexes. Ab initio calculations predict a very large barrier height for all six molecules in the order 1 (919 cm⁻¹) ≈ 3 (913 cm⁻¹) > 2 (847 cm⁻¹) > 4 (608 cm⁻¹) ≈ 5 (603 cm⁻¹) ≈ 6 (599 cm⁻¹), suggesting larger barrier heights for Cp ring systems, followed by six-membered arene systems and then corannulene. DFT based molecular dynamics calculations were performed on complexes 3, 5 and 6. For complexes 3 and 5, the geometries that are dynamically accessible are far fewer. The range of U_eff computed for molecular dynamics snapshots is high, indicating a possibility of translating the large U_eff obtained into attractive blocking temperatures in these complexes, but the converse is found for 6. Furthermore, an in-depth C–H bond vibrational analysis performed on complex 3 suggests that the vibration responsible for reducing the blocking temperature in dysprocenium SIMs is absent here as the C–H bonds are stronger and corannulene steric strain prevents the C(Cp)–Dy–C(Cor) bending. As [(η⁶-corannulene)TM(X)]⁺ (TM = Ru, Zr, Os, Rh, Ir and X = C₅Me₅, C₆Me₆) are known, the predictions made here have a higher prospect of yielding stability under ambient conditions, a very large U_eff value and a high blocking temperature – a life-giving combination to new generation SMMs.

Bringing half-sandwich Dy(iii) SIMs under the umbrella of corannulene was found to offer stability, greater barrier height and may offer higher blocking temperatures.     

Fabrication of Phosphorus-Doped Cobalt Silicate with Improved Electrochemical Properties

The development of electrode materials for supercapacitors (SCs) is greatly desired, and this still poses an immense challenge for researchers. Cobalt silicate (Co₂SiO₄, denoted as CoSi) with a high theoretical capacity is deemed to be one of the sustainable electrode materials for SCs. However, its achieved electrochemical properties are still not satisfying. Herein, the phosphorus (P)-doped cobalt silicate, denoted as PCoSi, is synthesized by a calcining strategy. The PCoSi exhibits 1D nanobelts with a specific surface area of 46 m²∙g⁻¹, and it can significantly improve the electrochemical properties of CoSi. As a supercapacitor’s (SC’s) electrode, the specific capacitance of PCoSi attains 434 F∙g⁻¹ at 0.5 A∙g⁻¹, which is much higher than the value of CoSi (244 F∙g⁻¹ at 0.5 A∙g⁻¹). The synergy between the composition and structure endows PCoSi with attractive electrochemical properties. This work provides a novel strategy to improve the electrochemical performances of transition metal silicates.     

The Effects of Chemical Bonding at Subatomic Resolution: A Case Study on α-Boron

Similar to classical asphericity shifts, aspherical deformations of the electron density in the atomic core region can result in core asphericity shifts in refinements using a Hansen-Coppens multipolar model (HCM), especially when highly precise experimental datasets with resolutions far beyond sin(θ)/λ ≤ 1.0 Å⁻¹ are employed. These shifts are about two orders of magnitude smaller than their counterparts caused by valence shell deformations, and their underlying deformations are mainly of dipolar character for 1st row atoms. Here, we analyze the resolution dependence of core asphericity shifts in α-boron. Based on theoretical structure factors, an appropriate Extended HCM (EHCM) is developed, which is tested against experimental high-resolution (sin(θ)/λ ≤ 1.6 Å⁻¹) single-crystal diffraction data. Bond length deviations due to core asphericity shifts of α-boron in the order of 4–6·10⁻⁴ Å are small but significant at this resolution and can be effectively compensated by an EHCM, although the correlation of the additional model parameters with positional parameters prevented a free refinement of all core model parameters. For high quality, high resolution data, a proper treatment with an EHCM or other equivalent methods is therefore highly recommended.     

Large molecules in high-intensity laser fields

New research fields have opened up that are related to the interactions between molecules and high-intensity optical fields where the laser intensity ranges from 10¹²–10¹⁷ W cm⁻². A broad outline of this area will be described from the perspective of products and new techniques for beam generation. Studies of large molecules have begun and some examples are introduced herein. Parent ions with little fragmentation are found to form in the intensity region below 10¹⁶ W cm⁻². The formation of intact ions can be used in femtosecond laser mass spectrometry. In the intensity region above 10¹⁶ W cm⁻², electrons are stripped from the molecules by optical field ionization and the highly charged ions can undergo a Coulomb explosion. Coulomb explosions of benzene and C₆₀ have been demonstrated, and the mechanism can be analyzed by means of molecular dynamics simulations. A high intensity femtosecond laser beam can be converted to radiation sources of coherent VUV light, X-rays etc. and some possibilities for new chemical applications will be discussed.     

Experimental Determination and Computational Prediction of Dehydroabietic Acid Solubility in (−)-α-Pinene + (−)-β-Caryophyllene + P-Cymene System

The solubility of dehydroabietic acid in (−)-α-pinene, p-cymene, (−)-β-caryophyllene, (−)-α-pinene + p-cymene, (−)-β-caryophyllene + p-cymene and (−)-α-pinene + (−)-β-caryophyllene were determined using the laser monitoring method at atmospheric pressure. The solubility of dehydroabietic acid was positively correlated with temperature from 295.15 to 339.46 K. (−)-α-pinene, p-cymene, and (−)-β-caryophyllene were found to be suitable for the solubilization of dehydroabietic acid. In addition, the non-random two liquid (NRTL), universal quasi-chemical (UNIQUAC), modified Apelblat, modified Wilson, modified Wilson–van’t Hoff, and λh models were applied to correlate the determined solubility data. The modified Apelblat model gave the minor deviation for dehydroabietic acid in monosolvents, while the λh equation showed the best result in the binary solvents. A comparative analysis of compatibility between solutes and solvents was carried out using Hansen solubility parameters. The thermodynamic functions of Δ_solH⁰, Δ_solS⁰, Δ_solG⁰ were calculated according to the van’t Hoff equation, indicating that the dissolution was an entropy-driven heat absorption process. The Conductor-like Screening Model for Real Solvents (COSMO-RS) combined with an experimental value was applied to predict the reasonable solubility data of dehydroabietic acid in the selected solvents systems. The interaction energy of the dehydroabietic acid with the solvent was analyzed by COSMO-RS.     

Chemical Variability and In Vitro Anti-Inflammatory Activity of Leaf Essential Oil from Ivorian Isolona dewevrei (De Wild. & T. Durand) Engl. & Diels

The chemical variability and the in vitro anti-inflammatory activity of the leaf essential oil from Ivorian Isolona dewevrei were investigated for the first time. Forty-seven oil samples were analyzed using a combination of CC, GC(RI), GC-MS and ¹³C-NMR, thus leading to the identification of 113 constituents (90.8–98.9%). As the main components varied drastically from sample to sample, the 47 oil compositions were submitted to hierarchical cluster and principal components analyses. Three distinct groups, each divided into two subgroups, were evidenced. Subgroup I−A was dominated by (Z)-β-ocimene, β-eudesmol, germacrene D and (E)-β-ocimene, while (10βH)-1β,8β-oxido-cadina-4-ene, santalenone, trans-α-bergamotene and trans-β-bergamotene were the main compounds of Subgroup I−B. The prevalent constituents of Subgroup II−A were germacrene B, (E)-β-caryophyllene, (5αH,10βMe)-6,12-oxido-elema-1,3,6,11(12)-tetraene and γ-elemene. Subgroup II−B displayed germacrene B, germacrene D and (Z)-β-ocimene as the majority compounds. Germacrene D was the most abundant constituent of Group III, followed in Subgroup III−A by (E)-β-caryophyllene, (10βH)-1β,8β-oxido-cadina-4-ene, germacrene D-8-one, and then in Subgroup III−B by (Z)-β-ocimene and (E)-β-ocimene. The observed qualitative and quantitative chemical variability was probably due to combined factors, mostly phenology and season, then harvest site to a lesser extent. The lipoxygenase inhibition by a leaf oil sample was also evaluated. The oil IC₅₀ (0.020 ± 0.005 mg/mL) was slightly higher than the non-competitive lipoxygenase inhibitor NDGA IC₅₀ (0.013 ± 0.003 mg/mL), suggesting a significant in vitro anti-inflammatory potential.     

Comparison of the effects of visible femtosecond laser pulses and continuous wave laser radiation of low average intensity on the clonogenicity of Escherichia coli

To evaluate the contribution of local pulsed heating of light-absorbing microregions to biochemical activity, irradiation of Escherichia coli was carried out using femtosecond laser pulses (λ = 620 nm, τ_p=3 × 10⁻¹³ s, f_p = 0.5 Hz, E_p = 1.1 × 10⁻³J cm⁻², I_av = 5.5 × 10⁻⁴ W cm⁻², I_p = 10⁹ W cm⁻²) and continuous wave (CW) laser radiation (λ = 632.8 nm, I = 1.3 W cm⁻²). The irradiation dose required to produce a similar biological effect (a 160%–190% increase in the clonogenic activity of the irradiated cells compared with the non-irradiated controls) is a factor of about 10³ lower for pulsed radiation than for CW radiation (3.3 × 10⁻¹ and 7.8 × 10² J cm⁻² respectively). The minimum size of the microregions transiently heated on irradiation with femtosecond laser pulses is estimated to be about 10 Å, which corresponds to the size of the chromophores of hypothetical primary photoacceptors—respiratory chain components.     

Sm0.5Sr0.5Co1−xNixO3−δ—A Novel Bifunctional Electrocatalyst for Oxygen Reduction/Evolution Reactions

The development of non-precious metal catalysts with excellent bifunctional activities is significant for air–metal batteries. ABO₃-type perovskite oxides can improve their catalytic activity and electronic conductivity by doping transition metal elements at B sites. Here, we develop a novel Sm_0.5Sr_0.5Co_1−xNi_xO_3−δ (SSCN) nanofiber-structured electrocatalyst. In 0.1 M KOH electrolyte solution, Sm_0.5Sr_0.5Co_0.8Ni_0.2O_3−δ (SSCN82) with the optimal Co: Ni molar ratio exhibits good electrocatalytic activity for OER/ORR, affording a low onset potential of 1.39 V, a slight Tafel slope of 123.8 mV dec⁻¹, and a current density of 6.01 mA cm⁻² at 1.8 V, and the ORR reaction process was four-electron reaction pathway. Combining the morphological characteristic of SSCN nanofibers with the synergistic effect of cobalt and nickel with a suitable molar ratio is beneficial to improving the catalytic activity of SSCN perovskite oxides. SSCN82 exhibits good bi-functional catalytic performance and electrochemical double-layer capacitance.     

Soy Isoflavones Inhibit Both GPIb-IX Signaling and αIIbβ3 Outside-In Signaling via 14-3-3ζ in Platelet

Soy diet is thought to help prevent cardiovascular diseases in humans. Isoflavone, which is abundant in soybean and other legumes, has been reported to possess antiplatelet activity and potential antithrombotic effect. Our study aims to elucidate the potential target of soy isoflavone in platelet. The anti-thrombosis formation effect of genistein and daidzein was evaluated in ex vivo perfusion chamber model under low (300 s⁻¹) and high (1800 s⁻¹) shear forces. The effect of genistein and daidzein on platelet aggregation and spreading was evaluated with platelets from both wildtype and GPIbα deficient mice. The interaction of these soy isoflavone with 14-3-3ζ was detected by surface plasmon resonance (SPR) and co-immunoprecipitation, and the effect of αIIbβ3-mediated outside-in signaling transduction was evaluated by western blot. We found both genistein and daidzein showed inhibitory effect on thrombosis formation in perfusion chamber, especially under high shear force (1800 s⁻¹). These soy isoflavone interact with 14-3-3ζ and inhibited both GPIb-IX and αIIbβ3-mediated platelet aggregation, integrin-mediated platelet spreading and outside-in signaling transduction. Our findings indicate that 14-3-3ζ is a novel target of genistein and daidzein. 14-3-3ζ, an adaptor protein that regulates both GPIb-IX and αIIbβ3-mediated platelet activation is involved in soy isoflavone mediated platelet inhibition.     

Square-Planar Heteroleptic Complexes of α-Diimine-NiII-Catecholate Type: Intramolecular Ligand-to-Ligand Charge Transfer

Two heteroleptic Ni^II complexes combined the redox-active catecholate and 2,2′- bipyridine ligand platforms were synthesized to observe a photoinduced intramolecular ligand-to-ligand charge transfer (LL’CT, HOMO_catecholate → LUMO_α-diimine). A molecular design of compound [Ni^II(3,6-Cat)(bipy)]∙CH₃CN (1) on the base of bulky 3,6-di-tert-butyl-o-benzoquinone (3,6-DTBQ) was an annelation of the ligand with an electron donor glycol fragment, producing derivative [Ni^II(3,6-Cat^gly)(bipy)]∙CH₂Cl₂ (2), in order to influence the energy of LL’CT transition. A substantial longwave shift of the absorption peak was observed in the UV-Vis-NIR spectra of 2 compared with those in 1. In addition, the studied Ni^II derivatives demonstrated a pronounced negative solvatochromism, which was established using a broad set of solvents. The molecular geometry of both compounds can be ascribed as an insignificantly distorted square-planar type, and the π–π intermolecular stacking of the neighboring α-diimines is realized in a crystal packing. There is a lamellar crystal structure for complex 1, whereas the perpendicular T-motifs with the inter-stacks attractive π–π interactions form the packing of complex 2. The redox-active nature of ligand systems was clearly shown through the electrochemical study: a quasi-reversible one-electron reduction of 2,2′-bipyridine and two reversible successive one-electron oxidative conversations (“catecholate dianion—o-benzosemiquinonato radical anion—neutral o-benzoquinone”) were detected.