一种基于序贯估计的直达声区水面舰船 被动测距方法 *

该文利用基于射线的盲解卷积方法，从直达声区的水面舰船噪声中提取出船和锚系于海底的垂直接收阵之间的时域信道响应，并利用直达波在不同阵元相对于参考阵元的到达时间差，通过序贯方法，利用射线模型和声速剖面信息，对水面舰船距接收阵的距离进行了估计。通过处理海深约为580 m的2016年美国圣巴巴拉海峡的实验数据，对1.6~3.5 km直达声区范围内Anna Maersk商船与垂直阵之间的距离进行了估计，验证了测距方法的有效性，并将结果与系统测量值和几何方法的估计值进行了比较。由于该方法不需要对海底参数进行估计，所以在海底参数未知时要优于传统匹配场方法；在声速剖面存在跃层且海底为多层分布的复杂信道条件下，该方法仍能对距离进行有效估计，且与测量值的相对误差在6%以内，小于几何方法的估计误差，测距结果精度较高。     

In‐Depth Understanding of the Chemical Properties of Rarely Explored Carbide Cluster Metallofullerenes: A Case Study of Sc2C2@C3v(8)‐C82 that Reveals a General Rule

The chemical properties of carbide‐cluster metallofullerenes (CCMFs) remain largely unexplored, although several new members of CCMFs have been discovered recently. Herein, we report the reaction between Sc₂C₂@C_3v(8)‐C₈₂, which is viewed as a prototypical CCMF because of its high abundance, and 3‐triphenylmethyl‐5‐oxazolidinone ( 1 ) to afford the corresponding pyrrolidino derivative Sc₂C₂@C_3v(8)‐C₈₂(CH₂)₂NTrt ( 2 ; Trt=triphenylmethyl). Single‐crystal X‐ray crystallography studies of 2 revealed that the reaction takes place at a [6,6]‐bond junction, which is directly over the encapsulated C₂ unit and is far from either of the two scandium atoms. On the basis of theoretical calculations and by considering previously reports, we have found that a hexagonal carbon ring on the cage of Sc₂C₂@C_3v(8)‐C₈₂ is highly reactive toward different reagents due to the overlap of high p‐orbital axis vector (POAV) angles and large LUMO coefficients. We propose that this highly concentrated area of reactivity is generated by the encapsulation of the Sc₂C₂ cluster because this region is absent from the empty fullerene C_3v(8)‐C₈₂. Moreover, the absorption and electrochemical results confirm that derivative 2 is more stable than pristine Sc₂C₂@C_3v(8)‐C₈₂, thus illuminating its potential applications.     

光电化学技术应用于抗氧化分析的研究进展

在新陈代谢过程中, 机体会产生大量以自由基为主要形式的氧化活性物质, 而抗氧化剂可以通过电子转移的方式捕获并中和自由基, 从而有效抵御自由基引起的细胞损害, 以保障和维护人体健康. 食品作为人体外源性抗氧化剂的重要来源可以有效补充因体内代谢及体液排出而损失的抗氧化物质, 因此对食品中抗氧化物质消除自由基的能力即抗氧化能力的测定和评价具有重要意义. 光电化学技术作为一种简单快捷、 低成本、 低背景且高灵敏度的测定方法, 能够有效克服光学法、 色谱法和电化学法等传统测试手段在抗氧化容量分析中的不足. 本文综述了基于半导体及其复合材料的光电化学传感平台的构建及食品体系抗氧化容量分析的研究进展, 评论了多种检测体系的特点并对其研究前景进行了展望.     

Few-Layer Fullerene Network for Photocatalytic Pure Water Splitting into H2 and H2O2

A few-layer fullerene network possesses several advantageous characteristics, including a large surface area, abundant active sites, high charge mobility, and an appropriate band gap and band edge for solar water splitting. Herein, we report for the first time that the few-layer fullerene network shows interesting photocatalytic performance in pure water splitting into H₂ and H₂O₂ in the absence of any sacrificial reagents. Under optimal conditions, the H₂ and H₂O₂ evolution rates can reach 91 and 116 μmol g⁻¹ h⁻¹, respectively, with good stability. This work demonstrates the novel application of the few-layer fullerene network in the field of energy conversion.     

Dearomative Ring-Fused Azafulleroids and Carbazole-Derived Metallofullerenes: Reactivity Dictated by Encapsulation in a Fullerene Cage

Herein, we report divergent additions of 2,2′-diazidobiphenyls to C₆₀ and Sc₃N@I_h-C₈₀. In stark contrast to that of the previously reported bis-azide additions, the unexpected cascade reaction leads to the dearomative formation of azafulleroids 2 fused with a 7-6-5-membered ring system in the case of C₆₀. In contrast, the corresponding reaction with Sc₃N@I_h-C₈₀ switches to the C−H insertion pathway, thereby resulting in multiple isomers, including a carbazole-derived [6,6]-azametallofulleroid 3 and a [5,6]-azametallofulleroid 4 and an unusual 1,2,3,6-tetrahydropyrrolo[3,2-c]carbazole-derived metallofullerene 5 , whose molecular structures have been unambiguously determined by single-crystal X-ray diffraction analyses. Among them, the addition type of 5 is observed for the first time in all reported additions of azides to fullerenes. Furthermore, unexpected isomerizations from 3 to 5 and from 4 to 5 have been discovered, providing the first examples of the isomerization of an azafulleroid to a carbazole-derived fullerene rather than an aziridinofullerene. In particular, the isomerism of the [5,6]-isomer 4 to the [5,6]-isomer 5 is unprecedented in fullerene chemistry, contradicting the present understanding that isomerization generally occurs between [5,6]- and [6,6]-isomers. Control experiments have been carried out to rationalize the reaction mechanism. Furthermore, representative azafulleroids have been applied in organic solar cells, thereby resulting in improved power conversion efficiencies.     

六聚吡咯/丝组缀合物结构的NMR和 ESI-MS/MS表征

利用片断合成法合成了具有DNA切割能力的六聚吡咯/丝组缀合物, 检测了该化合物的¹H、¹³C NMR 和ESI-MS/ MS 图谱, 确证了该化合物的结构, 通过¹H-¹H COSY, HSQC,HMBC等2D NMR 技术对其¹H 和¹³C NMR 数据进行了归属和解析, 并探讨了其ESI-MS/ MS 质谱裂解规律.     

面向产出的高分子化学课程教学大纲的构建*

基于工程教育认证的核心理念,制定了面向产出的高分子化学课程教学大纲。与传统课程教学大纲不同,本大纲的课程目标是使学生具备推演、阐述、分析和研究高分子材料领域复杂工程问题的能力,体现以学生为中心、面向产出和持续改进的理念。课程教学内容既包含知识点又包含能力要求,强调课程知识点与学生能力达成的支撑关系。在课程考核部分,提出了分目标模块化的考核方法和评分标准,满足了工程认证可衡量、易操作的考核要求。     

N''-(2-羟基-5-甲氧基苯甲基)-4-二甲氨基苯甲酰肼及其氧钒(Ⅴ)配合物:合成、晶体结构和脲酶抑制活性

制备了一个苯甲酰腙化合物N'-(2-羟基-5-甲氧基苯甲基)-4-二甲氨基苯甲酰肼(H₂L)。利用H₂L、乙酰氧肟酸(HAHA)和VO(acac)₂在甲醇中反应得到了配合物[VOL(AHA)]。通过元素分析、红外和紫外光谱,以及单晶X-射线衍射对H₂L和其配合物进行了表征。苯甲酰腙配体作为二价阴离子,利用其酚羟基氧原子、亚胺基氮原子、以及烯醇氧原子与V原子进行配位。乙酰氧肟酸配体利用其羰基氧原子和去质子化的羟基氧原子进行配位。配合物中的V原子为八面体配位构型。测试了H₂L、HAHA和钒配合物的脲酶抑制活性。在浓度为100μmol·L^-1时,钒配合物对幽门螺旋杆菌脲酶的抑制率为63%,其IC₅₀值为45μmol·L^-1。还利用分子对接技术研究了配合物分子与脲酶的作用方式。     

超高效液相色谱-串联质谱法测定烟用水基胶中邻苯二甲酸酯类化合物

建立了一种测定烟用水基胶中17种邻苯二甲酸酯类(PAEs)化合物的超高效液相色谱-串联质谱(UPLC-MS/MS)法。样品经水分散,以甲醇定容,涡旋振荡萃取。萃取液离心后,过有机相滤膜进行UPLC-MS/MS分析。通过增加延时柱的方法,排除色谱系统带入的PAEs干扰。结果表明:在0~5μg/m L范围内,方法的线性关系良好,相关系数均大于0.994,定量下限为0.010~0.479μg/g。该方法的回收率为87.6%~106.0%,相对标准偏差(RSD,n=6)为0.8%~6.2%。将该方法与YC/T 333-2010标准方法进行对比,结果显示两种方法的检测数据不存在显著性差异。方法用于烟用水基胶中17种PAEs的测定,操作简单,稳定性好。