N2H4在NiFe(111)合金表面吸附稳定性和电子结构的第一性原理研究

采用基于色散校正的密度泛函理论进行了第一性原理研究, 详细分析了肼(N₂H₄)在Ni₈Fe₈/Ni(111)合金表面稳定吸附构型的吸附稳定性和电子结构及成键性质. 通过比较发现, 肼分子以桥接方式吸附在表面的两个Fe原子上是最稳定的吸附构型, 其吸附能为-1.578 eV/N₂H₄. 同时发现, 肼分子在这一表面上吸附稳定性的趋势为: 桥位比顶位吸附更有利, 且在Fe原子上比在Ni原子上的吸附作用更强. 进一步分析了不同吸附位点上稳定吸附构型的电子结构、电荷密度转移以及电子局域化情况. 结果发现: 相同吸附位点的电子态密度图基本一致, 并且N原子的p轨道和与之相互作用的表面原子的d轨道之间存在态密度上的重叠; 吸附后电荷密度则主要从肼分子转移到表面原子之上; 在电子局域化函数切面图中也发现吸附后电子被局域到肼分子的N原子和相邻的表面原子之间. 这些电子结构的表征都充分说明肼分子与表面原子之间通过电荷转移形成了强烈的配位共价作用.     

Dysprosiacarboranes as Organometallic Single-Molecule Magnets

The dicarbollide ion, nido-C₂B₉H₁₁²⁻ is isoelectronic with cyclopentadienyl. Herein, we make dysprosiacarboranes, namely [(C₂B₉H₁₁)₂Ln(THF)₂][Na(THF)₅] (Ln=Dy, 1Dy ) and [(THF)₃(μ-H)₃Li]₂[{η⁵-C₆H₄(CH₂)₂C₂B₉H₉}Dy{η²:η⁵-C₆H₄(CH₂)₂C₂B₉H₉}₂Li] 3Dy and show that dicarbollide ligands impose strong magnetic axiality on the central Dy^III ion. The effective energy barrier (U_eff) for the loss of magnetization can be varied by the substitution pattern on the dicarbollide. This finding is demonstrated by comparing complexes of nido-C₂B₉H₁₁²⁻ and nido-[o-xylylene-C₂B₉H₉]²⁻, which show a U_eff of 430(5) K and 804(7) K, respectively. The blocking temperature defined by the open hysteresis temperature of 3Dy reaches 6.8 K. Moreover, the linear complex [Dy(C₂B₉H₁₁)₂]⁻ is predicted to have comparable properties with the linear [Dy(Cp^Me3)₂]⁺ complex. As such, carboranyl ligands and their derivatives may provide a new type of organometallic ligand for high-performance single-molecule magnets.     

Monochromophore-Based Phosphorescence and Fluorescence from Pure Organic Assemblies for Ratiometric Hypoxia Detection

Hypoxia is a parameter related to many diseases. Ratiometric hypoxia probes often rely on a combination of an O₂-insensitive fluorophore and an O₂-sensitive phosphor in a polymer matrix, which require high cost and multi-step synthesis of transition metal complexes. The two-chromophore hypoxia probes encounter unfavorable energy transfer processes and different stabilities of the chromophores. Reported herein is a pure organic ratiometric hypoxia nanoprobe, assembled by a monochromophore, naphthalimide ureidopyrimidinone (BrNpA-UPy), bridged by a bis-UPy-functionalized benzyl skeleton. The joint factors of quadruple hydrogen bonding, the rigid backbone of UPy, and bromine substitution of the naphthalimide derivative facilitate bright phosphorescence (Φ_P=7.7 %, τ_P=3.2 ms) and fluorescence of the resultant nanoparticles (SNPs) at room temperature, which enable accurate, ratiometric, sensitive oxygen detection (K_sv=189.6 kPa⁻¹) in aqueous solution as well as in living HeLa cells.     

Ultrastable Surface-Dominated Pseudocapacitive Potassium Storage Enabled by Edge-Enriched N-Doped Porous Carbon Nanosheets

The development of ultrastable carbon materials for potassium storage poses key limitations caused by the huge volume variation and sluggish kinetics. Nitrogen-enriched porous carbons have recently emerged as promising candidates for this application; however, rational control over nitrogen doping is needed to further suppress the long-term capacity fading. Here we propose a strategy based on pyrolysis–etching of a pyridine-coordinated polymer for deliberate manipulation of edge-nitrogen doping and specific spatial distribution in amorphous high-surface-area carbons; the obtained material shows an edge-nitrogen content of up to 9.34 at %, richer N distribution inside the material, and high surface area of 616 m² g⁻¹ under a cost-effective low-temperature carbonization. The optimized carbon delivers unprecedented K-storage stability over 6000 cycles with negligible capacity decay (252 mA h g⁻¹ after 4 months at 1 A g⁻¹), rarely reported for potassium storage.     

Cross-Module Enoylreduction in the Azalomycin F Polyketide Synthase

The colinearity of canonical modular polyketide synthases, which creates a direct link between multienzyme structure and the chemical structure of the biosynthetic end-product, has become a cornerstone of knowledge-based genome mining. Herein, we report genetic and enzymatic evidence for the remarkable role of an enoylreductase in the polyketide synthase for azalomycin F biosynthesis. This internal enoylreductase domain, previously identified as acting only in the second of two chain extension cycles on an initial iterative module, is shown to also catalyze enoylreduction in trans within the next module. The mechanism for this rare deviation from colinearity appears to involve direct cross-modular interaction of the reductase with the longer acyl chain, rather than back transfer of the substrate into the iterative module, suggesting an additional and surprising plasticity in natural PKS assembly-line catalysis.     

Separation of micro and sub-micro diamagnetic particles in dual ferrofluid streams based on negative magnetophoresis

In the present study, we numerically demonstrate an approach for separation of micro and sub-micro diamagnetic particles in dual ferrofluid streams based on negative magnetophoresis. The dual streams are constructed by an intermediate sheath flow, after which the negative magnetophoretic force induced by an array of permanent magnets dominates the separation of diamagnetic particles. A simple and efficient numerical model is developed to calculate the motions of particles under the action of magnetic field and flow field. Effects of the average flow velocity, the ratio of sheath fluid flow to sample fluid flow, the number of the magnet pair as well as the position of magnet pair are investigated. The optimal parametric condition for complete separation is obtained through the parametric analysis, and the separation principle is further elucidated by the force analysis. The separation of smaller micro and sub-micro diamagnetic particles is finally demonstrated. This study provides an insight into the negative magnetophoretic phenomenon and guides the fabrication of feasible, low-cost diagnostic devices for sub-micro particle separation.     

Bucillamine Inhibits UVB-Induced MAPK Activation and Apoptosis in Human HaCaT Keratinocytes and SKH-1 Hairless Mouse Skin

Ultraviolet B (UVB) radiation is known as a culprit in skin carcinogenesis. We have previously reported that bucillamine (N-[2-mercapto-2-methylpropionyl]-L-cysteine), a cysteine derivative with antioxidant and anti-inflammatory capacity, protects against UVB-induced p53 activation and inflammatory responses in mouse skin. Since MAPK signaling pathways regulate p53 expression and activation, here we determined bucillamine effect on UVB-mediated MAPK activation in vitro using human skin keratinocyte cell line HaCaT and in vivo using SKH-1 hairless mouse skin. A single low dose of UVB (30 mJ cm⁻²) resulted in increased JNK/MAPK phosphorylation and caspase-3 cleavage in HaCaT cells. However, JNK activation and casaspe-3 cleavage were inhibited by pretreatment of HaCaT cells with physiological doses of bucillamine (25 and 100 µm ). Consistent with these results, bucillamine pretreatment in mice (20 mg kg⁻¹) inhibited JNK/MAPK and ERK/MAPK activation in skin epidermal cells at 6–12 and 24 h, respectively, after UVB exposure. Moreover, bucillamine attenuated UVB-induced Ki-67-positive cells and cleaved caspase-3-positive cells in mouse skin. These findings demonstrate that bucillamine inhibits UVB-induced MAPK signaling, cell proliferation and apoptosis. Together with our previous report, we provide evidence that bucillamine has a photoprotective effect against UV exposure.     

基于偶氮苯衍生物的三阶非线性光开关性能的调控

偶氮苯衍生物因其具有特殊的共轭体系常用作光开关特性的三阶非线性光学（NLO）开关材料,但有部分带有特殊基团的偶氮类分子在一般条件下无法显示其性能.然而,这类分子在被调节之后能展示出优异的光控的NLO开关性能.以无光控的NLO开关性能的5-（N-4-偶氮苯基）氨甲基间苯二甲酸为研究对象,并对其潜在的光控NLO开关性能进行调控.经过调节后的这类分子在光照条件下能顺利地经历可逆的顺反异构化反应,且产生三阶非线性性能的转换.其Z-扫描实验结果显示处于反式构型的材料展示出反饱和吸收和自散焦特性;在光照之后,这类材料转化为顺式构型并展现出饱和吸收和自聚焦行为.三阶NLO性能的转换是由于材料的结构发生转变其内部电子产生重排,使得它们在激光刺激下产生不同的响应机制.     

Superwetting Patterned Membranes with an Anisotropy/Isotropy Transition: Towards Signal Expression and Liquid Permeation

Superwetting membranes with responsive properties have attracted heightened attention because of their fine‐tunable surface wettability. However, their functional diversity is severely limited by the “black‐or‐white” wettability transition. Herein, we describe a coating strategy to fabricate multifunctional responsive superwetting membranes with SiO₂/octadecylamine patterns. The adjustable patterns in the responsive region are the key factor for functional diversity. Specifically, the coated part of the membrane displayed a superhydrophobicity/superhydrophilicity transition at different pH values, whereas the uncoated part exhibited invariant superhydrophilicity. On the basis of this anisotropy/isotropy transition, the membranes can serve as either responsive permeable membranes or signal‐expression membranes, thus enabling the responsive separation and permeation of liquids with satisfactory separation efficiency (>99.90 %) and flux (ca. 60 L m^?2 h), as well as real‐time liquid signal expression with alterable signals.     

Effects of High-Intensity Ultrasound Pretreatment on Structure,Properties, and Enzymolysis of Walnut Protein Isolate

The purpose of this paper was to investigate the effect of high-intensity ultrasonication (HIU) pretreatment before enzymolysis on structural conformations of walnut protein isolate (WPI) and antioxidant activity of its hydrolysates. Aqueous WPI suspensions were subjected to ultrasonic processing at different power levels (600–2000 W) and times (5–30 min), and then changes in the particle size, zeta (ζ) potential, and structure of WPI were investigated, and antioxidant activity of its hydrolysates was determined. The particle size of the particles of aqueous WPI suspensions was decreased after ultrasound, indicating that sonication destroyed protein aggregates. The ζ-potential values of a protein solution significantly changed after sonication, demonstrating that the original dense structure of the protein was destroyed. Fourier transform infrared spectroscopy indicated a change in the secondary structure of WPI after sonication, with a decrease in β-turn and an increase in α-helix, β-sheet, and random coil content. Two absorption peaks of WPI were generated, and the fluorescence emission intensity of the proteins decreased after ultrasonic treatment, indicating that the changes in protein tertiary structure occurred. Moreover, the degree of hydrolysis and the antioxidant activity of the WPI hydrolysates increased after sonication. These results suggest that HIU pretreatment is a potential tool for improving the functional properties of walnut proteins.