Synthesis of C12-Keto Saxitoxin Derivatives with Unusual Inhibitory Activity Against Voltage-Gated Sodium Channels

A novel series of C12-keto-type saxitoxin (STX) derivatives bearing an unusual nonhydrated form of the ketone at C12 has been synthesized, and their Na_V-inhibitory activity has been evaluated in a cell-based assay as well as whole-cell patch-clamp recording. Among these compounds, 11-benzylidene STX ( 3 a ) showed potent inhibitory activity against neuroblastoma Neuro 2A in both cell-based and electrophysiological analyses, with EC₅₀ and IC₅₀ values of 8.5 and 30.7 nm , respectively. Interestingly, the compound showed potent inhibitory activity against tetrodotoxin-resistant subtype of Na_V1.5, with an IC₅₀ value of 94.1 nm . Derivatives 3 a – d and 3 f showed low recovery rates from Na_V1.2 subtype (ca 45–79 %) compared to natural dcSTX ( 2 ), strongly suggesting an irreversible mode of interaction. We propose an interaction model for the C12-keto derivatives with Na_V in which the enone moiety in the STX derivatives 3 works as Michael acceptor for the carboxylate of Asp¹⁷¹⁷.     

Reactivity of Diarylnitrenium Ions

Hydride abstraction from diarylamines with the trityl ion is explored in an attempt to generate a stable diarylnitrenium ion, Ar₂N⁺. Sequential H-atom abstraction reactions ensue. The first H-atom abstraction leads to intensely colored aminium radical cations, Ar₂NH^.+, some of which are quite stable. However, most undergo a second H-atom abstraction leading to ammonium ions, Ar₂NH₂⁺. In the absence of a ready source of H-atoms, a unique self-abstraction reaction occurs when Ar=Me₅C₆, leading to a novel iminium radical cation, Ar=N^.+Ar, which decays via a second self H-atom abstraction reaction to give a stable iminium ion, Ar=N⁺HAr. These products differ substantially from those derived via photochemically produced diarylnitrenium ions.     

介孔碳材料抑制锂电池负极枝晶生长

为了解决锂电池负极表面锂枝晶生长带来的性能衰退和安全问题。 以沸石咪唑酯骨架-8(ZIF-8)为前驱体制得介孔碳材料(MCM),用于金属锂负极表面改性。 X射线粉末衍射(XRD)和拉曼光谱表明,退火制得的MCM具有一定的石墨化程度,N₂气吸脱附测试(BET)证明MCM具有典型的介孔特征。 对比不同温度退火样品的XRD、拉曼光谱和BET测试结果,确定900 ℃为最佳退火温度。 优化的MCM作为表面改性剂对金属锂负极进行改性研究。 电池充放电循环后,负极样品的XRD和扫描电子显微镜(SEM)测试表明,MCM能够通过均衡锂负极表面的电荷分布抑制金属锂的取向沉积和锂枝晶的生长。 本研究为制备抑制锂电池负极枝晶生长表面改性剂提供了一种简便而有效的合成方法,有利于锂电池循环寿命的延长和安全性能的提高。     

基于有序介孔碳的氯离子选择性电极的制备及其在手持传感系统中的应用

以有序介孔碳(OMC)球为离子-电子转换层,制备了固态氯离子选择性电极,构建了基于离子敏感的场效应晶体管(ISFET)的手持式传感系统,用于检测人体血清中的氯离子。优化了OMC前驱体的碳化温度,探究了OMC形貌结构对电极传感性能的影响;电极柔性化制备后考察了其在手持系统中对氯离子的检测效果。结果表明,最优条件下,电极在5.12×10^-4~1.02 mol/L的浓度范围呈现线性响应,响应斜率为60 mV/decade。该柔性电极在手持传感系统中展现出高灵敏度和重现性,可用于人体血清样品中氯离子的检测,其回收率为96.3%~104.9%。     

Nucleon effective mass splitting and density-dependent symmetry energy effects on elliptic flow in heavy ion collisions at E_(lab)= 0.09 ～ 1.5 GeV/nucleon

By incorporating an iso spin-dependent form of the momentum-dependent potential in the ultra-relativistic quantum molecular dynamics(UrQMD) model,we systematically investigate effects of the neutron-proton effective mass splitting m*_(n-p)=m*_n-m*_p/m and the density-dependent nuclear symmetry energy E_(sym)(ρ) on the elliptic flow v_2 in~(197)Au+~(197) Au collisions at beam energies from 0.09 to 1.5 GeV/nucleon.It is found that at higher beam energies(≥0.25 GeV/nucleon) with the approximately 75 MeV difference in slopes of the two different E_(sym)(ρ),and the variation of m*_(n-p) ranging from-0.03 to 0.03 at saturation density with isospin asymmetry δ=(ρ_n-ρ_p)/ρ-0.2,the E_(sym)(ρ) has a stronger influence on the difference in v_2 between neutrons and protons,i.e.,v_2~n-v_2~p,than m*_(n-p) has.Meanwhile,at lower beam energies(≤0.25 GeV/nucleon),v_2~n-v_2~p is sensitive to both the E_(sym)(ρ) and the m*_(n-p).Moreover,the influence of m*_(n-p) on v_2~n-v_2~p is more evident with the parameters of this study when using the soft,rather than stiff,symmetry energy.     

Heterointerface Engineering of ZnO/CdS Heterostructures through ZnS Layers for Photocatalytic Water Splitting

Solar-driven water splitting to produce clean and renewable hydrogen offers a green strategy to address the energy crisis and environmental pollution. Heterostructure catalysts are receiving increasing attention for photocatalytic hydrogen generation. ZnO/ZnS/CdS and ZnO/CdS heterostructures have been successfully designed and prepared according to two different strategies. By introducing a heterointerface layer of ZnS between ZnO and CdS, a Z scheme charge-transfer channel was promoted and achieved superior photocatalytic performance. A highest hydrogen generation rate of 156.7 μmol g⁻¹ h⁻¹ was achieved by precise control of the thickness of the heterointerface layer and of the CdS shell. These findings demonstrated that heterostructures are promising catalysts for solar-driven water splitting, and that heterointerface engineering is an effective way to improve the photocatalytic properties of heterostructures.     

Addition of SiO2 to the operation of a polyimide cathode in a sodium battery

The effect of the addition of SiO₂ nanoparticles on the properties of a polyimide cathode was explored by CV, XPS, and galvanostatic cycling methods. The capacity and average cycling potential of the cell increased in the presence of SiO₂. By quantum chemical modeling, it was shown that SiO₂ nanoparticles served as a framework for polyimide, which retained its fixed structure upon metalation with sodium.     

An Ion-Exchangeable MOF with Reversible Dehydration and Dynamic Structural Behavior (NH4)2[Zn2(O3PCH2CH2COO)2]⋅5 H2O (BIRM-1)

(NH₄)₂[Zn₂(O₃PCH₂CH₂COO)₂]⋅5 H₂O (BIRM-1) is a new metal phosphonate material, synthesized through a simple hydrothermal reaction between zinc nitrate and 3-phosphonopropionic acid, using urea and tetraethylammonium bromide as the reaction medium. In common with other metal–organic framework materials, BIRM-1 has a large three-dimensional porous structure providing potential access to a high internal surface area. Unlike most others, it has the advantage of containing ammonium cations within the pores and has the ability to undergo cation exchange. Additionally, BIRM-1 also exhibits a reversible dehydration behavior involving an amorphization-recrystallization cycle. The ability to undergo ion exchange and dynamic structural behavior are of interest in their own right, but also increase the range of potential applications for this material. Here the crystal structure of this new metal phosphonate and its ion exchange behavior with K⁺ as an exemplar are studied in detail, and its unusual structure-reviving property reported.     

Arylpyrrolyldiketone Boron Complexes Exhibiting Various Anion‐Binding Modes Based on Dynamic Conformation Changes

Arylpyrrolyldiketone boron complexes as anion‐responsive π‐electronic molecules were synthesized by Claisen condensations of acetylpyrrole and corresponding aryl esters. The synthesized π‐electronic molecules exhibited anion‐binding behavior with various binding modes including pyrrole‐inverted and non‐inverted [1+1]‐type anion complexes as well as [2+1]‐type complexes owing to the presence of only a single pyrrole ring. Furthermore, solid‐state ion‐pairing assemblies, comprising receptor–anion complexes and countercations, were constructed based on fairly planar [2+1]‐type complexes.